Organic C h e m i s t r y . Explosive Double Salt of Potassium Cyanide and Potassium Nitrit4. By KARL A. HOFJIANN (Zeit. aizorg. Chew, 1895, 10, 259- 26l).-A good yield of sodium nitroferrocyanide is obtained by the action of a concentrated solution of ferrous sulphate on an aqueous solnt,ion containing equal weights of.' sodium iiitri te and potassj urn cyanide. TVitli the object of obtaining nn intermediate COmpouiid, which, by the action of ferrous sulphate, is converted into the nitro- ferrocyanide, tlle author has examined the action of potassium cyanide on potassium iiiti-ite. When a solution of the two salts is boiled, the cycznide is converted into ammonia, and potassium carbonate, formate, and nitrate. The do.rible saZt, KCN,KN02 + +H,O, is obtained by dissolving potassium nitrite (50 grams) aiid potassium cyanide (20 grams) in the smallest possible quantity of water and allowing the solution to eva- porate over sulphuric acid.Potassium cyanide separates first, and then the new double salt in short, characteristic prisms. It explodes with a loud report when heated at 4U0-500°, but does not explode 09 percussion ; on recrystallisation in a vacuum over sulphuric acid, it is partially decomposed into its component salts. With silver nitrate, the neutral solution gives silver cyanide and silver nitrite. E. C. R. Sodium Nitroferrocyanide. By KARL A. HOFJIAW (Zeif. army. Chem.., 1895, 10, 262-276) .--Sodi.rcm rLmidofer.1.ocyanide, FeC5N6 H,Na&H20, is obtained by reducing sodium nitroferrocyanide with 4 per cent. sodium amalgam9 cooling the mixture with ice and salt ; the product is precipitated with alcohol, re-dissolved in ice-cold water, and again precipitated.It crystallises in bright yellow needles, and its solii- tion decomposes at the ordinary temperature yielding ammonia, ferric hydroxide, and sodium ferrocyanide. With bleaching powder and dilute sulphuric acid, it gives a beautif a1 reddish-violet solution ; with ferrous sulphate, a bright greenish-blue precipitate ; with ferric chloride, a deep blue-green precipitate ; and with dilute hydrochloric acid, a green solution. When heated with sodium hydroxide, it yields ammonia, ferric hydroxide, and sodium ferrocyanide; when heated with hydroxylaniine and cli lute sodium hydroxide, it gives a reddish-yellow, and then .?I beautiful, bluish-red solution.The same compound is also obtained when a solution of s0diu.m nitroferrocyanide, cooled with ice and salt, is treated with gaseous ammonia; the product obtained crystallised, however, with GH2O. The silver salt, FeC,N6H2Ag3,3H20, is obtained in white aggregatas by addiug silver nitrate to the aqueous solution in the presence of neutral ammonium nitrate ; when treated with methylic iodide, decomposition takes place, and it residue, containing iron and cyaiiogen together with methyl- carbg lamine, is formed. T h2 forrna tion of amidoferrocyanide from 9. VOL. LXX. i,70 ABSTRACTS OF CHEXICAL PAPERS. nitrofei*rocyanide is a reduction process and not a substitution pro- ccss ; for amidoferrocyanide is formed, by the action of mono- and di- eth-j-lamine, a s well as by that of ammonia.When preparing the compound by the action of these ;\mines, hydrates, with 5H,O and 7H,O, were obtained. When nitroferrocyanide is treated with pure trirnethylamine, a brisk evolution of nitrogen takes place, and sodium ferrocpnide and ferric hydroxide are formed ; when a 10 per cent. alcoholic solution of triinethjlamine is eniployed, amidoferrocyanide is formed. Sodium amidoferrocyanide is either not altered or entirell- decomposed by acetic anhydride, benzenesulphonic chloride, alcohol and carbon bisulphide or chloroform. When treated with iodine dissolved in potassium iodide or in alcohol, i t gives a beautiful violet- red compound which easily decomposes into sodium ferrocyanide, ferI+ hydroxide, nitrogen,and ammonia.If contiiiuously oxidised with potas- sium permailgarlate in a1 kaline solution at the tempei-ature of melting ice, it yields sodium nitroferrocyanide. When treated with nitric oxide in ice-cold aqueous solution, i t jields the sodium ni troferrocyauide, FeCbN,Ntt10zH,7H,0, which crystallises in yellow needles, a i d loses 4+ mols. of water when allowed to remain over sixlphuric acid a t 50'. When the amidoferrocyanide (6 grams) is treated with sodium nitrite (1.2 grams) in ice-cold aqueous solution, and then acidified with acetic acid, a brisk cvvlut'ion of gas, containing nitric oxide: takes place, and the solution turns violet-red ; when this solution is made slightly alkaline and precipitated with alcohol, the conpmud, (Na,FeC,N,),NOKa, + 16Hz0, is obtained.It crjstallises in beautiful orange-j-ellow needles, gives an intense violet coloration with monium sulphide, and does not yield ammonia when heated with sodiuiii hydroxide. When treated with sodinni nitrite and acetic acid in ice-cold solution, it is converted into sodium nitroferi-ocpnide. If only 0.95 gram sodium nitrite is used for 6 grams of sodium amicio- ferroGyanide, the compound, (Na,FeC,N,)JYH, 16H20, is obtained ; this cyystallises in sulphur-yellow plates, gives a beautiful bluisli-red solution with hydroxylamine and sodium hydroxide, a greenish-blue precipitate with ferrous chloride, an intensely blue precipitate with ferric: chloride, and a violet solution with sodium nitrite and acetic acid. When heated with sodium hydroxide, it yields ammonia, and with small quantities of sodium nitrite it yields sodium nitroferro- cyanide.Frorii the abore reactions, the author points outl that the amido- group in amidoferrocyanides behave in a very different manner from anlido-groups in organic compounds, and he coiicludes that it is com- bined with iron as expressed in the formula NHz*Fe(CN),Na,, E. C. R. Action of Carbonic Anhydride, Water, and Alkalis, on Solu- tions of Cyanuric acid and Alkali Cyanurates. By PAUL LEMOULT (Cmnppt. rend., 1895, 121, 404-406) .-Thermochemical considera- tions indicate that carbonic anhydride should displace sodium from trisodium cyanurat,e and convert the latter into the monosodium salt, and experiment confirms this conclusioii, the monosodium salt, being precipitated when the gas is passed into a concentrated solution ofORQANIC CBEMISTRY.71 the trisodiurn sait. Further, carbonic anhydride precipitates the acid from a concentrated solution of t h e monosodium salt. Direct experiment shows that, in aqueous solution, cyanuric acid is slowly converted into ammonia and carbonic anhydride. It is also found that the residue of thermal effect observed when the acid is neutralised with an alkali is much reduced if neutralisation is effected as rapidly as possible, but is greatly increased if the addition of successive equivalents of a1 kal i is extended over several hours. These rcsults confirm the author’s view that the apparent residual heat of neutralisation i s a consequence of tohe partial decomposition of the acid (this vol., ii, l l ) , this decomposition being accelerated by the presence of an alkali.Bivalent Carbon : Chemistry of Cyanogen and Isocyanogen. By JOHK U. NEF (Aimden, 1895,287, 265-359; compare Abstr., 1895, i, 3 and Y).-The author’s previous investigations on the subject of bivalent carbon have dealt with aromatic and aliphatic members of the isocyanide group, which are represented by the general formula R.N:C, and with fulniinic acid, wliich is expressed constitutionally by the formula CNOH. Attention is now directed towards cyanogen and iso- cyanogen: and regarding as possible the existence of three isomeric substances having the empirical formula C2N2, namely, cyanogen, N.C.CiN, cyanisocyanogen, N.C*N:C, and diisocyanogen, C:N*N:C (Thiele, Abstr., 1894, i, Cl), the author claims to have established by his experiments the conclusion that the cyanides are derivatives of isocysnogen, and that hydrogen cyanide itself mnst henceforth be looked on as hydrogen isocyanide, HN:C.Tlie foundation for this view is strengthened by the striking resemblance between the salts of hydroxyisocyanogen (fulminic acid) and derivatives of hydrogen isocyanide, the similarity being in some cases so close as to have given rise occasionally to confusion between the substances them- selves. If potassium cyanide is, in yeality, potassium isocysnide, KN:C, the chemical activity of an unsaturated compound will be displayed by this substance, it having been shown (Abstr., 1892, 1438) that the more positive the character of an unsaturated molecule, the more readily will additive compounds be obtained from it.It is shown by the author’s investigation that potassiuni cyanide does actually exhibit such behaviour, forming ethylic cjanimidocarbonate when treated in dilute, aqueous solution with ethylic hypochlorite i this reaction is analogous to the conversion of isonitriles into derivatives of mesoxamide by means of carbonyl chloride (Abstr., 1892, 14:33). Ethylic cyanimidocarhonate, C:N*C(NH ).OEt, is obtained by add- ing ethylic hypochlorite (9 grams) to a solution of potassium cyanide (18 grams) in five times the quantity of water, the liquid being con- stantly agitated, and maintained at a temperature of -10’. After adding about half the quantity of ethylic hypochlorite, the colour- less solution becomes tnrbid owing to the separation of an oil, which is extracted with ether and dried with calcium chloride ; on remov- ing the solvent, a n oil is obtained having sweet, but penetrating odour, and on distiiling this substance the greater part boils a t C.H. B. 9 272 ABSTRACTS OF CHEMICAL PAPERS 3-51' under a pressure of 30 mm., the higher fraction passing over at 80' under a pressure of 26 mm., and solidifging in the con- denser. The liquid is ethylic cganimidocarbonate, the solid being ethylic diimidoxalate, which is produced from the former compound by the action of alkali. Ethylic cyanimidocarbonate is a colourless oil having a sweet, but penetrating odour; it is sparingly soluble in cold water, and has the sp. gr. = 1.00 a t 15". It boils at 42', SO', and 60°, under pressures of 20 mm., 30 mm., and 42 mm., respectively, and when distilled under atmospheric pressure, hoils, and slightly decomposes at 133'.After st few days it darkens and ultimately becomes almost black, but the greater part can be recovered on distillation. Pro- longed digestion on the water bath with alcoholic potash or sodium ethoxide converts the substance into potassium cyanide, alcohol, and potassium cyanate ; aqueous alkalis give rise to ethylic diimidoxalate, alkali cyanide and cyanate. Ethylic cyanimidocarbonate is decom- posed by hydrochloric acid into ammonium chloride and ethylic cyanocarbonate; when heated with aniline on the water bath, it yields ammoiiia, hydrogen cyanide, alcohol, and ammonium cyanide, whiIst from the portion of the residue insoluble in cold alcohol, ethylic acetate extracts cyananiline.A'thylic dii?nidoxu?ate, OEt.C(NH )*C(NH)*OEt, is obtained by the action of dilute alkalis on ethylic cyanimidocarbonate ; it forms heavy colourless crystals which gradually become brown ; melts at 38" and has a slightly sweet, peculiar taste. The subsfdnce was obtained in an impure state by Pinner and Klein (Ber., 1878, 11, 1437), who passed cyanogen into alcoholic hydrochloric acid ; their preparation was brown and melted at 25'. The pure substance boils at 69", 80°, and 100Ounder pressures of 18 mm., 32 mm., and 82 mm., respectively ; under atmospheric pressure it boils and slightly deconi- poses at 172". It dissolves readily in water at 2 5 O , and on cooling the liquid at 5' it solidifies to a magma of white needles consisting of a hydrate which contains 11H20 ; it dissolves with difficulty in cold ether and water at 12', calcium chloride cotnpletely removing aatei- from the ethereal solution.Mercuric chloride produces a white, in- soluble precipitate when added to aqueous et hylic diimidoxalate. Ethylic diimidoxalate is not converted into a derivative of oxalic acid on treatment with aqueous alkalis, but on adding dilute hydro- chloric acid to the salt, heat is developed, ammonium chloride and ethylic oxalate being produced ; aniline at the temperature of the water bath gives rise to cyananiline. Ethylic imidocarbonate, HN:C(OEt),, is obtained by adding ethylic diimidoxalate (25 grams) to an alcoholic solution of sodium ethoxide containing 4 grams of sodium, filtering from sodium vyanide which separates at 60°, and extracting with ether the dilated liquid after treatment with caustic potash; it boils at 62' and 77' under pressures of 36 mm., and 80 mm.respectively, and when distilled under atmospheric pressure, boils and slightly decomposes at 138-140". The sp. gr. = 0.948 a t 23'. Ethylic imidocarbonate has been obtained in an impure state by Snndmeyer, from potassium cyanide, canstic soda, alcohol and chlorine; it is also prepared byORGANIC CHEMISTRY. 53 gently heating ethylic cyanimidocarbonate with alcoliolic sodium ethoxide. When ethylic inlidocarbonate is heated with alcoholic potash, potassinm cyanate is formed ; aqueous alkalis are without action on the substance. Btlq Zic iwtidoza Za t e, 0 E t o C NH) C 0 0 E t , is obtained by ag i t a tiag a solution of ethylic diimidoxalate (48 grams) in water (240 grams) with decinormal hydrochloric acid (333 gi-anis), and extracting the clear, neutral solution with ether; i t boils at 73' nnder a pressure of 18 mm., and under atmospheric pressure a t 175", when i t decom- poses.Mercuric chloride yields a white precipitale with an aqueous solution of the substance. Very dilute hydrochloric acid converts ethylic monimidoxalate into etliylic oxalate ; the hydrochloride of ethylic oxalate is formed when hydrogen chloride is passed into the solution in dry ether, and it is also obtained on submitting ethylic cyanocarbonwte to the same treatment. Sodium cjanide and ethylic carbonate are produced when ethylic monimidoxalate is treated with alcoholic sodiurn ethoxide a t - 10".Alcoholic sodium ethoxide at - 10" decomposes benzoic cyanide into ethylic benzoate and sodium cyanide, the same agent converting ethFlic cyanocarbonate into hydrogen cyanide and ethj-lic carbonate ; alcoholic hydilogen chloride, however, coriverts these substances into ethylic benzoylformate and ethylic iniidoxa late respectively. Ethylic cyanimidocarbonate is fci-med when cyanogen chloride or bromide acts on a dilute, nlcoholic: solution of potassiuni cyanide. When chlorine is led into a solution of potassium cyanide in dilute alcollol, cyanogen chloride, et hylic diimidoxalate, and ethylic cyan- imidocarhoLate are formed, the last named being convcrted by the alkali into ethylic imidocarbonate.On addiilg ethylic hrpochlorite to diliite alcoliolic potassiuni cyanide a t - 7", ethylic diimidoxalate is for M ed . Reiizer/ eazo-ir,/ idofor my Z cyanide, pu' PhX* (3 (N H) *C iN , is the ye1 lo m substance obtained by Gabriel (Abstr., 1880,41) 011 adding a solution of diazo benzene chloride to potassium cyanide dissolved in water, and which he regarded as having the formula NPIi:N*CiN + HCN on account of ihe readiness with which hydrogen cpnide is eliminated ; the product of this decomposition is diazolnenzene cjanide, NPli:N-C:K (compare Abstr., 1895, i, 34s). Ethylic eth?lli~~?idocl~Zoi.ociii.boiiate, NEt:CCl*OEt, is obtained by adding dry ethylic hypochlorite at -5' to ethjlic isocyauide at -10 to - 1 5 O , in molecular proportion, and maintaining the tempera- ture of the mixture below O", it boils a t GSo and 68" under pressures of 58 mm.and 100 mm. respectively, and at 126" under atmospheric pressure. The vnpour has a penetrating odour resembling that of alkjlic isocyanates, and vigorously attacks the eyes. Water and dilute hydrochloric acid slowly decompose ethjlic ethylimidochloro- carbonate, giving rise to carboriic anhydride, ethylic chloride, diethjl- carbamide, and much ethylurethane. Alcoholic sodium ethoxide converts it into etlrylic ethyli~zidocnrbonate, which boils a t 147", and ethyylic eth~Zimidocyn~zoca~bollnte is obtained when ethylic ethylimido- chlorocarbonate is added to a solution of potassium cyanide in dilute74 ABSTRACTS OF CHEMICAL PAPERS. alcohol ; it is all oil which boils at 7t3' under a pressure of 82 mm., and has a sweet, penetrating odour. Ethylimidoch1ol.o-j~rmyl cyanide, NEt:CCl*CiN, is obtained by alIowing a mixture of cyanogen chloride and ethylic isocyanide, in molecular proportion, to remain in contact for two days, and then raising the temperature f w a few minutes to 70"; the portion dis- tilling between 120' and 130" is agitated with very dilute hydro- chloric acid, washed, dried, and 18edistilled.It is a colourless oil which boils a t 126O, and has a peneti-ating odour. Trimolecdar benzoic cyanide, [COPh*CN],, is obtained by heating benzoic bromide (21 grams), absolute ether (150 c.c.), and silver cyanide (20 grams) for 10 hours in a reflux apparatus from which moisture is excluded, and which is heated on a water bath a t 60'.After removing the ethereal liquid, aqueous pctassium cyaiiide is added to the yesidue in order to remove silver bromide, and the pro- duct is then dissolved in chloroform ; it crystallises f ~ o m hot benzene in pale yellow needles, and melts a t 195'. The substance is insoluble in water and ether, but dissolves readily in chloroform and hot ben- zene ; when heated at 300°, it decomposes, yielding benzonitrile. It may also be obtained from ordinary beuzoic cyanide by passing hydrogen bromide into the solntion in absolute ether. Dimolecular benzoic cyanide was obtained by Wache on heating an ethereal solution of benzoic cyanide with sodium ; it is also fcrmed when benzoic chloride is agitated a t -5'with a solution of potas- sium cyanide i n dilute alcohol. It ciystallises from alcohol in colour- less needles, and melts at 99--100° (Wache observed 95') ; undei- a, pressure of 15 mm.i t boils a t 220'. Ordinary benzoic cyanide is formed when benzoic anhydride and potassium cyanide in molecular proportion are heated a t 190'. When ethjlic chlorocarbonate (28.5 grams) is heated with silver cyanide (36.4 grams) f o r six hours a t 130-140', :I mixture of ethylic cyanocarbon~te and ethylic isocpanocarbonate is formed. Ethylic chlorocarbonate (50 grams), when agitated with a solution of potassium cyanide (32 grams) iii water (96 grams) and alcohol (25 grams), cooled at -13', yields ethylic cyanocarbonate and a small quantity of ethylic carbonate ; i f action proceeds at ordinary temperatures, less ethylic cyanocarbonate is formed, a substance being produced which, in the presence of water o r alkalis, yields hydrogen cyanide, potassiiim chloride, carbonic ail hydride, and alcohol. On agitating a solution of potassinm cyanide in 6 parts of water cooled at - 10' or - 15' whilst carbonyl chloride is slowly added, an additive compound is formed which breaks up spontaneously into hydrogen cyanide, potassium chloride, and potassium carbonate.I n 1857 CloEz obtained from cyanogen chloride and alcoholic sodium ethoxide, an oil which he regarded HS ekhylic cyanate (Conyt. rend., 44, 482), and this result was confirmed by Hofmann and Olshausen (Be,.., 2870, 3, 269) ; subsequently Muldcr observed that the action of cyanogen bromide on sodium etlioxide in presence of water gave rise to urethane and the substalice isolated by Cloih, which, how- ever, has the composition OEt*CN,HOEt, and also a considerable quan- tity of ethylic cjannurate.Finally, Ponomarefi (Abstr., 1832, 937) re-ORGANIC CHEblISTRY. 75 corded the formation of an oil which distilled between 90" and 200", and had a basic odour which disappeared on heating the product in an open basin on the water bath. The author finds, in the first place, that pure cyanogen bromide is without action a t 50" on sodium ethoxide suspended in absolute ether and free from alcohol : cyanogen chloride is equally inert, but if alcoholic sodium ethoxide is added to cyanogell bromide or chloride a t -S' to -lo", a rise of temperature takes place, and the sole product is ethylic imidocsrbonate ; if the action proceeds a t ordinary temperatures, the yield of ethylic imido- carbonate is diminished, urethane and ethylic cyanurate being formed in small quantity.Ethylic imidocarbonate is produced with a small quantity of urethane when excess of caustic soda OY potash is added to a mixture of cyanogen chloride (or bromide), water ( 5 parts), and alcohol (2 parts) cooled to -5" or -lo", the temperature of the liquid being maintained below 0' ; these substances probably a&e from the decompositio~i by water or alcohol of the intermediate pro- duct NH:CCI*OEt. When hydrogen bromide is passed into a solution of cyanogen bromide in absolute ether, a yellowish-whit,e precipitate of imidocarbonyl bromide, NH:CBr2, or the hydrobromide, is formed ; i t is hsgroscopic, and fumes in air, yielding carbonic anhydride and ammonium bromide, whilst, in a dry atmosphere, hydrogen bromide is elimirinted atld cyanogen bromide formed.Phenylic ii,iidocurbonate, NH:C( OPh),, is obtained by adding a solution of phenol (80 grams) and caustic potash (48% grams) in 300 C.C. of water to a solution of c*yanogen bromide (46 grams) in 6500 C.C. of water at 20°, and crystallises from petroleum in colour- less needles melting at 54'; it is insoluble in water, but dissolves readily in organic solvents, excepting petroleum. Dilute hydrochloric acid converts it, into phenylic carbonate and animonium chloride, the action of alcoholic potash gives rise to potassium cyanate, and when heated alone in a dry tube, phenylic imidocarbonate yields phenol and phenylic cyanurate.The observation of Hofmann and Olshausen (loc. cit.), who passed cyttnogen chloride into alcol~olic sodium plienoxide and obtained phenylic cyanurate, is incorrect, neither t h i s substance nor phenylic cyanate being formed ; when an alcoholic solution of cyaiiogen chloride or bromide is treated with aqueous or alcoholic sodium pheiioxide, plienylic imidocarbonate is the chief product, eflzylic plzenylic indocnrtoizate being also formed ; the latter boils at 120" under a pressure of 18 min. The observa- tion of Hofmaiin and Olshansen originates in the fact that both this salt and also phenylic iniidocarbonate decompose into phenol and phenjlic cpnurate when heated a t 180". When cyanogen is passed into an ice-cold solution of potassium cyanide in dilute alcohol, ethylic cyaniniidocarbonate is formed together with n small quantity of ethylic diimidoxalate ; when passed into a solution of sodium et'lioxide in alcohol a t 0", ethylic diimid- oxalste is the sole product.The author has devised a method of obtaining hydrogen cyanide in the pure siate. The slightly itbnoi*mal vapour density of former preparations is probably due to the presence of about 2 per cent. of ammonium cyanide, and to remove this impurity, dry hydro-76 ABSTRACTS OF CHEMICAL PAPERS. gen cyanide obtained from potassium ferrocyanide a1.d sulphuric acid is distilled from phosphoric anhydride, and the rapour, after pa~siiig through a tube maintained at 40-50' containing a mix- ture of glass beads and pliosplior~c anhjdride, enters a long con- denser, the distillate being collected in a recciver and protected from moisture by a long tube containing cnlcinni chloride and pliosphoric anhydride.The product boils a t 25" {corr.), and melts a t -12O to -loo, undergoing no change when preserved for many months in closed vessels ; the purest specimen previously obtained boiled a t 26' (con.), and melted at -14" (Gautier). I n comparison with its salts and the alkylic isocyaaides, hydrogen cyanide is a very inert sub- stance ; it does not combiDe with chlorine or hydrogen chloride at lorn temperatures, and no action takes place when it remains in con- tact with ethylic hypochlorite for a protracted period a t -10". The want of harmony among the statements of prcvions investigators (Pinner, Abstr., 1883, 731 arid 1089 ; and 1895, i, 264 ; Lengfeld and Stieglitz, Abstr., 1895, i, 277 ; and Clnisen and Matthews, f j e y ., 188:3, 16, 311), has led the author to study the action of hydrogen chloride on hydrogen cyanide in presence of alcohol, with the result that the following observations hare been made. Imidoformyl chloride, NH:CHCI, is first formed, a2d unites with hydrogen cyaxide form- ing the compound NH:CH*C(NH)Cl, which takes up one or two inoleculai* proportions of hydrogen chloride ; in presence of alcohol, the product gives rise to the compound OEt-CH(NH2)*CCl(NH,)*OEt, which is present in the mixture of salts which Pinner obtained. The intermediate compound, NH:CH*C(NH)Cl, also yields ethylic diethoxyiniidoglyoxylate, CH (OEt),*CCl (SHH?) *OE t, and et hxlic diethox-~ortliamidoglyoxylate hydrochloride, CH(OEt)z-C (OEt)2*NH,,HCl.This brief 'summary is much expanded in the original paper, which contains a theoretical discussion of the results obtained. Imidofo~myl cyanide, NH:CH*C':N, is prepared in the following manner. Pinner's salt, ethylformimide hydrochloride (Zoc. cit.), ob- tained by passing hydrogen chloride into a mixture of alcohol with a solution of hydrogen cyanide in absolute er;her, is suspended in ether and treated with caustic soda; after remora1 of solid matter, and evaporation of the ether, an oil is deposited which is a mixture of irnidoformyl cyanide, the dialcoholate, and cthylic diethoxyorth- amidoglgoxylate. On distillation under reduced pressure the cyanide solidities in the condenser.Imidoformyl cyanide melts at 8 7 O , and boils at 120-125' without decomposing ; it is extremely volatile, and sublimes in closed vessels. The substance is clecomposeci by caus tic soda or dilute hydrochloric acid, yielding ammonia and formic acid, whilst an aqueous solution quick!y decomposes when heated in a sealed tube at looo, yielding formamidine formate and ammonium forniate ; agitation with caustic soda and benzoic cliloride gave rise to benzamide and dibenzoyl formamidine. The s i l v e ~ derivative of the hydrate of iniidoforniyl cyanide, AgC2N2H,H20, is formed on adding silver nitrate t o the concentrated aqueous solution ; i t is crj-stalline and colourless, becoming black when treated with boiling water.ORGANIC OHEMISTRY. 77 On heating hydrogen cyanide (10 grams) with acetic anhydride (37.4 grams) in a sealed tube for five hours a t 190--2OO", diacetjldi- cyanide is formed.When hydrogen cyanide (15 grams) remains in con- tact with acetic bromide (45.5 grams) for f o u ~ weeks a t the ordinary temperature, n hygroscopic substance is formed which decomposes on treatment with water into hydrogen cyanide, acetic acid, 2nd hydrogen bromide ; i t probably consists of pyruvimide bromide, NH:CBr*C OMe. The paper concludes with a theoretical discussion of the results described. M. 0. F. Compounds of Acetone with Polyhydric Alcohols. By AR'r HI: R s YE 1 E It (Bey., 1 &%, 28, 253 1-2 5 34) .-Dimetone- ery thrit ol, c4H604(c3H6)2, prepared by Fischer's method (Abstr., 1895, i, 441) from acetone and erythritol, has a bitter tast'e, melts at 56", and boils at 1O5-l0(io (pressure = 29 mm.). Diacetonearabitol, C5HE0,(C3F~,),, is a, colourless syrup with a bitter taste, and may be distilled under diminished pressure.Diacetone-adonitol is also a syrup which has a bitter taste, and boils at 150-155° (pressure = 1 7 mm.). Diacetone-dzdcifoZ, CsH,,Os( C3H6)*, crystallises in prisms, melts at 9so, aud boils a t 193-195" (pressure = 18 mm.). T~.iaceto?ae-so?.bitoZ, C6H80,( C3H,),, is a colourless, crystalline mass, which melts a t about 40°, and boils at 170-175° (pressure = 25 mm.). Friacetone-2- ylucoheptitol, C,H,,,0,(C3H6)3, is a thick, faintly yellow syrup, which has a bitter taste, and boils a t 200--201° (pressure = 24 mm.). Acetone is thus seen to react much more uniformly with the higher nlcoliols thau does benzaldehpde.A. H. Constitution of Pectins. By CHARLES F. CROSS (Ber., 1895, 28, 2609--2611).-According to Tromp do Haas and Tollens(this vol., i, 7), the atomic ratio of oxygen to hydrogen in the pectins is very nearly 1 to 2, and the percentage composition of nearly all the substances analysed is very similar t o that of the oxycellulose-cellulose series. One specimen of pectin had the composition of the typical limo- cellulose, jute fibre, and appears by its reactions to be a scliihle ligiiocellulose free froni the substances which usually bccompany lignncellulose and react with phloroglucinol and aniline salt.. l'lie pectins appear to be distillpished from ore another by differences which me quite analogous to those by means of which the various members of tile group of celluloses can be dislinguished.Preparation of Ethylamine from Aldehyde-Ammonia. BJ FERDIXAND JEAN ( B U Z Z . SOC. Chim., 1895, [ 3 ] , 13, 474; compare Cambiei- and Brochet, Abstr., 1895, i, 641, and this vol., i, 7).- Ethylaminc is readily obtained by reducing aldehyde-amnionia with zinc and hydrochloric acid by Trillat and Fayollat's method. The freshly prepared crystals (10 grams) are mixed with a little water and zinc dust (20 grams), and dilute hydrochloric acid (150 gixm5, 1 : 3) gradually added during 10 minutes; after the lapse of a further interval of 10 minutes, some concentrated acid (20 grams) is added, and the mixture kept cool at first, but after 45 minutes heated on a A. H.78 ABSTRACTS OF CHEMICAL PAPERS. water bath; the ethylamine is then liberated by adding sufficient caustic soda to redissolve the zinc hydroxide at first precipitated, and is separated by distillation with steam.The yield of the hSdrochloride is about 30 per cent. of the alde- hyde employed. As no appreciable amonnt of t,he amine is formed by the action of hydrochloric acid alone, the process seems to be pnrely one of reduction. JN. W. Hexamethylenetetramine Mercurochlorides and Mercur- iodide. By MARCEL DEL~PTNE (Bull. Soc. Chim., 1895, [3], 13, 49-97 ; compare Abstr., 1895, i, 444).-There are three mercurc- chlorides of hexamethylenetetramine. The first, CsH,,N4,2HgCI,,H,0, obtained by exactly precipitating the aqueous amine with aqueous mercuric chloride in the cold, forms silky, white needles, and is stable at loo", but at a higher temperature commences to decom- pose, finally melting at abont 208".It forms a yellowish, amor- phous additive compound xith 1 mol. of bromine a t the ordinary temperature. The second mercurochloride, C6Hl2Nd,HC1,2 HgC12,H20, resembles the first in appearance, and is formed in a similar manner from the hydrochloric acid solution of the amine ; it melts sharply at 165", but becomes solid ,again at a higher temperature, finally softening at about 210" to a yellowish-grey paste. T t also fornis an additive com- pound with bromine. The third naercurochlo~*ide, (C,H,,N,,'2HgC:,,H,O),,NH,CI,HgC 12,HZO, is prepared by adding a concentrated solutiou of mercuric chloride in ammonium chloride to a boiling solution of hexamethylene- tetramine containing ammonium chloride : a precipitate forms at first, but redissolves, and on cooling, the mercurochloride separates in hard, dense, colourless prisms. It is stable at loo", but commences to decompose a t about 168".All three mercurochiorides are hydrolysed by water at 100" into formaldehyde, mercuric oxide, and ammonium chloride, and the yellowish powder resulting from their decomposition a t a higher temperature consists chiefly of mercuric oxide. The mercuyiodide, C6H12N4,2Hg12,H20, is obtained by adding excess of a solution of potassium rnercuriodide in dilute acetic acid to the aqueous amine ; the solution is boiled until the precipitate redissolves, and the double salt separates in golden-yellow scales. It softens at 156", and melts at 165".JN. W. Compounds of Amidoguanidine with the Sugars. By HEINRICH WOWF (Uer., 1895, 28, 2613-2615 ; compare Abstr., 1894, i , 3 15) .-Gal a ctoseamidoguanidine ch lovide forms rho mbic cry stais, and is slightly dextrorotatory ; gulactoseamidoguanidine szrlphate also forms rhombic crystals, which are sparingly soluble in alcohol. Lactoseantidogz~anidiize sdphate crjstallises like the sulphate just described, and is dexti*orotatory ; the nitrate forms microscopicORGANIC CHEMISTRY. '79 needles, which melt and decompose at about 800'. obtained from the sulphates by means of baryta are amorphous. The free bases A. H. Thiamines. By FELIX LENGFELD and JUL~US STIEGLITZ (Be).., 1895, 28, 2742-2744 ; compare A bsti.., 1895, i, 864).-Thiethylirnine, (SXEt),, is prepared by the action of ethylamine (10 grams) dis- solved in light petroleum (150 grams) on recently prepared sulphur dichloride (7.5 grams) dissolved in light petroleum (20-30 grams). The solutions must be dry, as, in presence of moisture, dark-coloured compounds are formed ; the ethylanline li,ydrocLiloride is removed by filtration, aiid the light petroleum distilled under reduced pressure in it stream of nitrogen free from moistuiae, carbonic anhydride and oxygeii.The thioimitie is n pale-jellow, mobile oil, with an odoar recalling both those of carby lamine and mercaptans ; i t decomposes when heat,ed, and on stailding graclually darkens. Cryoscopic mole- cular weiglit deterriiinatiolis agree with the above formula. The l i g h t petroleum employed W'RS treated succesnively witli siilphur di- chloride, water, potash, dried wit 11 potassium Iiydroxide, and distilled, that portion boiling a t 39-40' being employed for the experiments ; unless these precnntions are adopted tlie petroleum yields a chloro- derivative in small quantity, which cannot be removed from the thio- i in i lie.J. B. T. Action of Hydroxylamine Hydrochloride on Isonitroso- acetone. By ILIiLoTtAD JOV~TSCH ITSCH (Ber., 1895,28,2673-2674) .-A yellow, amorphous mass is obtained when isonitrosoacetone (acetone- oxime) is warmed with an aqueous solution of hydroxylaaiine hydro- chloride ; when recrystallised from water, itl forms small, colourless needles, and melts and decomposes at 245-246'. It has the composi- tion CfiH9N303, is readily dissolved in alkalis yielding a yellow solu- tion, and gives precipitates with solutions of most of the heavj metals.When hydrolysed with 30 per cent. sulphuric acid at 140°, i t gives acetic acid, formic acid, r? hydroxylamine salt, and ammonia. The substance, C6H9N303, is identical with that obtained by Scholl (Abstr., 1891, 287), and tlie autlioi* has discoutinu2d his investigation. J. J. S. zxp-Trihalogen Butyric acids from the Geometrically Iso- meric a-Halogen Crotonic acids. By VICTOR VALENTIN (Bey., lS95, 28, 2661-2665).- Both a-cllorocrotnnic acids, when sus- pended in carbon irisulphide, readily absorb chlorine, and foim the ax/3-trichlorobu t.yric acid previously described by Kramer and Pinner ( B e y . , 3, 389), Judson (ibid., 785), and Garzat*olli-Thurnlakh (this .Journal, 1876, ii, 623).Wlien warmed, the sodium salt of this acid rapidly decomposes, evolving carbonic nnliydride, and giving Judson's aa-dichloropropylenc. axp-Tribromobutyvic acid may be obtained in a similar manner by the addition of 2 atoms of bromine to either of the a-bromocrotonic acids (Micliael a n d Pentlleton, Abstr., 1888, 1176) ; an aqueous solution of the sodium salt of tlie tribromo-acid readily evolves carbonic anliydride, and yields m-dibt.omopropyletie. When the latter is hentecl for I d lmnrs a t 150' with excess of alcoholic potash, i t is almost cntlreiy coriverted into alljlene. J. J. S .89 ABSTRACTS OF CHEMICAL PAPERS. a-Dimethylamidocaproic acid. By ?DOCARD T)L-VILLIEK (Bull. SOC. Chim., 1895, [3], 13, 484-4S7) .-a-Dimethglamidocaproic acid is formed by heating a-bromocapi*oic acid with aqueons dimethyl- amiiie (2 niols.) in a sealed vessel a t 100'.the liberated hydrobromic acid combining with the second molecule of the aniine ; the product is boiled with bargta water to expel the excess of the amine, and the acid obtained by decomposing its silver salt, or better, its copper salt with hydrogen snlphide. a-Dintrth ylrrnzidocapnic acid, CH,Pr-CH( NMe,)*COO H + 2H20. crpstallises in bundles of needles, and is freely soluble in water and alcohol, b u t insoluble in ether ; when hcated, it melts and sublimes, but at the same time decomposes; the melting point is not giren. The coppel. salt, with 2H20, cr~-st;illises in dai-k blue plates or scales, and melts a t ZLO", hut neither t!le zinc nor the cadmium salt seeins to be capable of existence.The pltztinocldoride forms sm:dl, clino- rhomhic, orange prisms, and melts a t 108", at the same time decom- posing slightly ; the azirochlomle resembles lead iodide in appearance, a i d a crystalline 1.ydrochZol-ide also appears to exist. Behaviour of the Alkali Salts of the Fatty Acids and of Soaps in presence of Water. By FI~IEDRICH KRAE'YT and H. \VIGI,OM (ller., 1895, 28, 256ti-2573, %73-2582).-11 I. The Soaps as C~ys- tnZloiJs.--When hot 1 per cent. aqueous solutions of sodium stearate, pa Imi tate, mjristnte, Iaurate, eh'iclwte, and oleate are allowed to cool, crjstals begin to form respectively at 60") 45", 31*5", ll", 35O, and O", that is, a t temperatures 9.2". 17', 23", 3P6", 16", and 14" below the melting points of the corresponding acids.The crystals consist of a mixture of the normal and acid salts ; when deposited fro171 more dilute solutions, the crystals co1lt:iin a smaller pi-oportion of sodiuni, whilst from x 5 pel- ceiit. solution of sodiuiii oleate, the neutral salt separates unchanged I If the hot aqueous solutions are satiiratcd with c;irboiiic anhydi*ide and allowed t o cool. the acid salts separate out ; for example, sodium h j drogeii palmitate, C16H: 10LNa,C16H3?02. 'I'he teniperature rtt \I hich any one of these separates lies above the melting l'oint of the ('orre- sponding acid, but below that of the sodiuiii IIFdrogen salt. 1V. The Socqx as Collozds.-'l'lic soaps Iiavt: keen examined n i t L respect to the extent to which they raisc the boiling point of water in Becknuann's appitratue.dodiuill wetate m d propionate act as if each molecule were dissol iated into two ; but, curiously enough the molecular weight, as cntculated from the observed rise of the boiling point, does not increase with iucreasing concentration, but actually diminishes With sodium capreate, a slight increase is oberl-cd ; but in very strong solutions the tl~ern~ometer actually begins to sink again, a i d the solution solidifies, on cooling, t o a gelatinous mass. Sodium iioiiylate and laurate are coiuparati vely little dissociated in ioodei ately dilute soliitions, and their inolecular weights incwase with increasing concentration to about double the theoretical. Sodium palmitate, stearatt), and oleate a t first produce n rise in tbe boiling point, but erentuall~-, a5 the solutions become more concentrated, the thermometer falls t o the boiling point of the JN.W.ORGANIC CEEMISTRY. 61 water used, and the solutions solidify on cooling to gelatinons masses. The soaps, then, iuider these circumstances, do not raise the boiling pDint of water in which they are dissolved, and, so far, exhibit the be!iaviour of collo'id substances such as gelatin and starch. C. F. B. Derivatives of p-Chlorocrotonic acid. By WL. SZENIC and R. TACGESELL (Ber., 1895, 28, 2665-2672).-Both Geuther's j3-chlorocrotonic acids (Zeit. fuy Chemie, 1871, 240), when dissolved in carbon bisulphide, readily absorb chlorine, and yield a&'3-trichloro- hittyric acid, which crystallises in rhombic plates, and melts at 51-5-52'.It is only sparingly solnble in water, but readily in alcohol, ether, bepzene, &c. If an aqueous solution of the tri- chlorinated acid is treated witb granulated zinc and leftJ for several weeks, a mixture of the zinc salts of ,@-chloroisocrotonic: acid and /3-chlor ocrotonic acid is formed. A solution of sodium trichloro- butyrate, when heated at loo', evolves carbonic anhydride and yields ~~-dichloropropylene ; the latter readily absorbs chlorine, and yields a tetrachloropropane which is ideutical with that obtained by Borsche and Fittig (A?mlnZen, 133, 114) by the action of phosphorus pents- chloride on unsymmetrical dichloracetone. By treating the a&3- trichlorobutyric acid with alcoholic potash, a mixture of two isomeric dichlorocrotonic acids is obtained ; the one which is formed in larger quantity melts at 75-5', and is the centric sym- metrical ap-dichlorocrotor& acid.The one formed in smaller quantity melts at. 92', and is identical with the ap-dichlorocrotonic acid obtained by the addition of two atoms of chlorine to tetrolic acid ; it must, therefore, be the plane symmetrical isomeride. The acid melting a t 92' is readily converted into tetrolic acid when treated with zinc, whereas the acid melting at 7.5" is not. J. J. S. Action of Hydroxylamine Hydrochloride on Ethylie Iso- nitrosoacetoacetate. By MILORAD JOVITSCHITSCH (Ber., 1895, 28, '2675-2683) .-By warming ethylic isonitrosoacetoacetate with hydroxylamine hydrochloride, the author has obtained a substance which crystallises in colourless, glistening plates, turns red at 120°, and is completely decomposed at 141-142' ; it is readily soluble in ethei- and in alcohol, sparingly in water, and quite insoluble in light petroleum.It dissolves in alkalis, yielding a deep red solution, but is decomposed when boiled with excess of potassium hydroxide, yielding hydrogen cFanide and the substance C8H9N3O3, this vol., i, 79. Aqueous sulphuric acid also decomposes the compound, yielding hydroxylamine and the compound CsHgN303. The author terms the substance oximidomethylisoxazololte, >C:N*OH, and thinks it is identical with the subst2ance previously described by Ceresole and Koeckert (Abstr., 1884, 1120) and by Nussberger (Abstr., 1892, 1175). The silver derivative is obtained as a red, crystalline precipitate on the addition of silver nitrate to the solution of the oxazolone or of its salts.The red precipitate usually contains YCMe 0--co82 ABSTRACTS OF CECEMLCAL PAPERS. more or less of a colourless silvei- salt mixed with it ; this colourless salt is more readily soluble in nitric acid than the red one, and the two may be separated by this means. The red salt is explosive, especially when previously heated for some time at 100'. The colourless salt is silver izormal diiso?zit?.o,~obutyl.ate ; i t readily explodes, and also turns black when heated with water. Wlien warmed with an alkali carbonate, the oximidomethylisoxazolone is rapidly converted into diisonitrosobutyric acid, tlie silver s a l t of which, when oxidised with nitric acid (sp.gr. 1*3), yields the peroxide of diisonitrosobutyric acid previously described by Angeli ( A hstr., 1893, i, 310). The silver salf crystallises in colourless plates, and is explosive ; the etltylic sulf may be obtained by oxidising ethylic diisonitrosobutyrate with nitric acid ; it is a thick, oily substance which boils a t 240-242'. When silver oximidomethylisoxazolone is oxidised with nitric acid, a small quantity of Angeli's acid is obtained, together with tlie silver salt of an isomeric acid. This silver salt crjstallises from water in silky needles. The corresponding acid, CdB4N2O4, differs from Angeli's acid in being only sparingly soluble in ether, in containing no watei of crystallisation, anti in the sweet taste of its sodium salt. The following formulze are given for tlie various acids :- Gale-- :COO€€ S.Me-1C;.(COOH) $Me*CH(KO2)*?0 N*OH 0H.K N.0-O-N N-- 0 Syn-diisonitrosobutpic Angeli'a pcroxidc acid. Xitroinethylisoxazolonc. J. J. S. acid. Preparation of Ethylic Isonitrosoacetoacetate and of an Isomeride from E thylic Acetoacet ate. By MIL o RA D JU v 11's c H IT s c II (Bey., 1895,28! 2683-2687 ; compare Abstr., 1878,396 ; 1882,949 and 1052).-The author recommends the following method for the prcpara- tion of ethylic isonitrosoacetoacetnte. Sodium nitrite (1 mol.) is inti- mately mixed with ethylic ecetoncetate (1 mol.), and to the well-cooled mixture 18 per cent. sulphiiric acid (+ mol.) is slowly run i l l ; after dilution with water, 'the solutioii is extracted with ether, the ether evaporated, aud the residue dissolved in light petroleum, this solution is then dried with anhydrous sodium sulphate, and, on evaporation, gives a 90 per cent.yield of the isoiiitroso-compound. When oxidiscd with nitric acid containing nitrous acid, it yields ethylic oxixnidonitroacetate (Abstr., 1895, i, 447), which can also be obtained in small quantities directly from ethylic acetoacetate by the action of nitric acid (sp. gr. 1.4) and a small quantity of sodium nitrite in the cold. The chief product of this action, however, is the componnd ?*N:?.CooEt (Cramer, Abstr., 1892, 699), which the author terms 0.N:C-COOEt ethylic perozydiisonitl.ososzLcci?zate. If, in the above reaction, a n excess of sodium nitrite is used, the product formed is a yellow oil, which does not crystallise and has the same percentage composition as ethylic isoilitrosoacetoacetate. It differs from its isomeride in the ease with which it is decomposed by dilute alkali, yielding a yellow solu tion.With hydroxylamine hydrochloride, it yields oxiniidomethyl-ORGANIC CHEMISTRY. 83 isoxazolone ; on oxidation, it gives the same products as ethylic iso- nitroaoacet&e, and, with phenylliydraziiie hydrochloride, it yields 4-oximido-3 : 1-methylphen~lpy~*azolone. The new isonieride can also be prepared by the action of nitrous acid on ordinary ethylic isoni t rosoacetoaceta te. The author considers the two compounds as s y n - and aiiki- isomerides accordiiig to Hantzscli's terminology. The new com- pound is ethglic syn-isonitroeortcetoacetate, arid the old cornpound is tile anti-isomeride.When treated with bromine (1 niol.), the two compounds yield the correspondiug monobroi~~o-der.ivatires ; these are both oils, but differ in their action with alkalis. J. J. S. Preparation of the Oxime of Ethylic Acetoacetate and its Derivatives. By ROBERT SCHIFF (Bes.., 1895, 28, 2731-2734).- Ethylic acetoacetate and aniline are dissolved a t the ordinary teni- perature in concentrated aqueous solution of hydroxylamine Iiydro- chloride (all in molecular proportion) ; when cool, the solution is extracted with ether, arid on evaporating the latter the oxinze remains as a reddish oil, which slowly changes into a ci.ystitlline condensation product melting a t 124.5-125'. If, instead of extracting with ether, the solution is saturated with sodium carboilate, acetoacetic aniiide oxime, NOH:CMe*CH2*CO*NHPh, is formed ; it has been receutly prepared by Know and Reuter (Abstr., 1894, i, 371). Etliylic EMe-fi*CooEt', is obtained by the action N*OH N*OH ace toacetate amphidioxime, of sulphuric acid (30 per cent.) and sodium nitrite O:I the monoxime ; contrary to the statement of Nussberger, it gives, with cupric acetate, a brown coloration and then a brox;n precipitate.NHPh*N:C - C0/O7 '' prepared by treating the solution of ethylic acetoacetate, aniline, and hydroxylamine hydrochloride, as above, with hydrochloric acid and sodium nitrite (compare Know and Reu ter, Zoc. cit.). Benzylitletbe- vMe:N>O, is obtained by any of the ketomethyl isozazolom, following methods : (1) simple mixing of the oxime and benz- aldehyde, (2) saturation of an ethereal solution of the oxime and aldehyde with hydrogen chloride, (3) addition of concentrated hydro- chloric acid to a mixture of the oxime and aldehyde, (4) addition of fuming hydrochloric acid to a mixture of the aldehyde and acetoacetic anilide oxime.The first method is the least, the third generally the most, satisfactory. The compound, whicli is deposited in pale yellow, lustrous crystals, softens a t 1 3 9 O , melts and in part decomposes at 14l0, and is extremely stable towards acids, being precipitated un- changed from concentrated sulphuric acid 011 dilution. I t is readily soluble in sodium carbonate solution, in potash, a i d in ammonia, and, if the solution has nol been unduly heated, it is reprecipitated OIL the addition of ail acid; if boiled with ammonia for a short time, however, the compound is conipletely decomposed, benxaldehgde being regenerated.Its solubility in alkalis suggests that in their presence the ?Me:N\ . Ketomethylisoxazolone phenylhydrazone, CHPh:C-CO84 ABSTRACTS OF CHEXlCAL PAPERS. isoxazolone ring is resolved, the acid N0H:CNe.C (CHPh)*COOH being formed. J. B. T. Crystallised Lactic acid of Constant Boiling Point. By FRIEDRICH K n a ~ ~ r and W. A. Dyes (Ber., 1895, 28, 2589-259i).- T h i s may be obtained by drying the commercial acid-best of sp. gr. 1.16-for a meek or two in a ('i vacuum) desiccator, and distilling it twice under apressure of 12.15 mm., obtained by means of the water pump, The distillation flask should have a capacity of 60-80 c.c., ancl should not be more than half filled ; the side tube should be wide and as low in the neck as possible, and the receiver should be kept at a temperature of 90-100° to prevent the condensation of water in i t ; the liquid is first heated in a water bath at '70" t,o drive off water, and then the residual acid is distilled as rapidly as possible, being heated by a small, rather smoky flame kept in motion under the flask.The product obtained in this way contains 99-99.5 per cent. of the acid; it boils at. about 122' under IA-15 mm., at 119-120" under 13-14 mm., and at 82-85' under 0.5-1 mm. pres- sure ; when cooled, it solidifies to white crystals which melt at about 1 8 O , and it is very hygroscopic. c'. F. B. Formation of Carbon Chains : Alkylation of Ethylic Malonate and Acetoacetate.By CARL A. BISCHOFF (Ber., 1895, 28, 2616- 2631).-The velocity of formation of the alkyl derivatives of ethylic malonate and acetoacetate cannot be deduced simply from the time which elapses before the reacting mixtnre of ethereal salt, sodium eth- oxide, and alkylic iodide,oT bromide assumes a neutral reaction, because several other reactions may occur which also lead to a condition of neutrality. Thus, the following may all take place : (1) hydrolysis of the original ethereal salt, (2) hydrolysis of the ethereal salt pro- duced, (3) production of an ether of the alkyl group, (4) elimination of the halogen combined with hydrogen, (5) exchange of the alkyl group of the et,hereal salt with that of the iodide added.It is there- fore necessary to determine experimentally in each case the amount of the " normal " product obtained. For the purposes of comparison, the author numbers the chain of atoms of the normal product in order, beginning with that carbon atom of the alkyl group which is most remote from the niethylene group of the original ethereal salt, and proceeding as shown in the accompanying scheme for ethylic isopropyl- malonate, 1 2 1 c yc c~c*o*co*c*co*o*c*c. 1 6 5 4 3 4 5 6 7 The course of the reaction is fouiid to depend on the presence of carbon atoms at the positions 1-5 and 1-6 ; the more carbon atoms there are in these positions, the less readily does the " normal " reac- tion proceed. Iu many cases, moreover, the iodide reacts more readily than the bromide.These results are in agreement with the author's " dynamical theory." Dericatires of ethylic: malonate ; the numbers express the percentage of the theoretical The following are t b e experimental details.ORGANIC CHEMISTRY. 85 amount which is experiment,ally obtained. Methyl-, 70-SO per cent., propyl-, 61--75 per cent. ; the bromide gives t h e better yield ; ethyl-, 73-80 per cent. ; isopropyl-, 77-83 per cent. ; butjl-, about 20 per cent. ; isobutyl-, 20-40 per cent. ; psendobutyl-, the " normal " pro- duct was not formed either from the chloride or iodide under the usual canditions ; traces were produced under R pressure of 5 atmos. ; isoamyl-, about 25 per cent. ; tertiary amyl-, the " normal " product, wag only formed in very small quantity ; allyl- good yield.Methjlic malonnte gives a yield of 75 per cent. of the methyl derivative. Derivatives of ethylic ucetoacctcite : Methyl-, 76 per cent. from the iodide, 46 per cent. from the bromide ; ethyl-, 60 per cent. ; propyl-, 72-78 per cent,. ; isopropyl-, the " normal " product is readllg formed from the iodide, but oiily in traces from the bromide; iso- butyl-, 66 per cent. from the iodide, only 6 per cent. from the bro- mide ; pseudobntyl-, the normal reaction does not occur when tlie chloride is used; isonmgl-, 75 per cent. ; tertiary amyl-, the normal reaction does not occur ; allyl-, 53-54 per cent. Action of Acetic Anhydride on the Acids of the Acetylene Series. By AR'rHUR MICEAEL and JOHX E. BUCHER (Be,.., 1895, 28, 2511-2512) .-Acetylenedicarboxylic acid is converted by acetic anhydride at 100" into acetoxymaleik anhydride, O A C * C < ~ ~ , ~ ~ , which melts at 89-91O ; alcohol converts this into ehhylic acetate and oxalacetate, whilst cold water produces tho corresponding acids.When cthylic dibromosuccinste, melting at 58O, is treated with sodium ethoxide, the product consists of about 80 per cent. of ethylic as-diethoxysuccinate, and 'LO per cent. of ethylic ethoxymaleate or ethoxyfnmamte. Both of these ethereal salts are converted by hydrolysis into the sodium salt of a diethoxyszsccinic acid, which loses the elements of ether when heated a t 100' or allowed to stand in a vaciium for some time, oxalacetic acid being formed. The same intermediate product is formed when Nef's ethylic ethoxy- fumarate (Abstr., 1893, i, 6%) is heated with alcoholic soda.Phenylpropiolic acid is converted by acetic anhydride i n t o a substance melting a t 'L53', which has the formula of phengl- propioliu anhjdride, but is probably the anhydride of a poly- meric dibasic acid. On reduction, this substance is converted into an acid which has the composition of the truxillic acids, bnt is not identical with any of the acids described by Liebermann. Action of Primary Aromatic Amines on Unsymmetrical Ketonic Compounds. By TAOUIS SIMON (Bdl. Soc. Chim., 1895, (3), 13, 474-484; compare Abstr, 1894, i, 509).-'l'he present instalment of the paper deals with the actioir of aniline on the alkglic pyruvates, including the ethylic, active amylic, isoamylic, allplic, and benzylic salts ; all these substances combine with aniline to form compounds of the type NPh:CMe*CO*CH2*C( COOR):NPh, A.H. co -0 COOH*CHz*C( OEt),*COOH, A. H. VOL. LXX. i. h86 ABSTRACTS OF CaENIOAL PAPERS. probably by condensation of two molecules of the nlkylic anilido- pyruvate, in a manner analogous to the condensation of aldehyde- aniline observed by von Miller and Plochl. Nthylic pyruvate is readily prepared by boiling the acid with alcohol in a reflux apparatus under ordinary pressure, and fractionat- ing the product under low pressure ; the yield is 90 per cent. of that indicated by theory, and the product particularly pure. Ethylic pyruvate is an almost colnurless liquid, resembling ethylic acetate in odour, and boiling a t 66" (18-20 mm.), and a t 155' nnder the ordinary pressure, in the latter case decomposing slightly ; the sp.gr. = 1.080 at 14" ; it is freely soluble in water, rapidly becoming hydroljsed into its proximate constituents. The hydrazone is identical with that prepared by Fischer from the hydrazone of pyruvic acid. The product of the condensation of ethylic pjruvate with aniline, CzoH2ONzO3, the molecular weight of which was determined by the cryoscopic method, is a white, crystalline solid, melting a t 146"; i t appears to foi-m two prodncts with phenylhydrazine, a white substaim melting at 55", and a yellowish-white substance melting at 119-120". Besides the more complex condensation product, some aniluvitonic acid (methylquinolinecarboxylic acid) is formed at the same time. Ethylic pyruvn te condenses with paratoluidine iri a similar manner, a stbbstance, C22HzJNZO3, being formed, which crystallises in colourless needles and melts a t 186' ; a t the same time, a second white crystal- line substance, melting at 140-14r3°, is produced.The condetzsation pyoduct of aniline with active amplic pyruvate melts at 110-1 I lo, and is unaccompanied by any other product. Issoamylic pyyuvate is prepared in the same way as the ethyIic salt ; i t is a limpid, yellowish liquid, having an odonr resembling t h a t of amylic acetate, and boiling at 86" (14 mm.), and at about 185' under the ordinary pressure ; sp. gr. = 0.978 at ISo. The phenylhydrazo~ce, which is very soluble in ether, melts at about 185-186". The product of the condensation of isoamylic pyruvate with aniline, C23Hz6Nz03, crystallises in well-defined needles, and melts at 126-127'.The condensation product with paratoluidine, C,,H,N,O,, melts at 1 4 0 O . Allylic pyruvate is prepared by passing hydrogen chloride into a mixture of the acid and the alcohol ; it is a colourless liquid, having a pungent odour, and boiling at 65" (14 mm.), and a t 165" under the ordinary pressure ; sp. gr. = 1.082 a t 17.5'. It unites with phenyl- hydrazine to form a yellow product melting at. l%", which does not appear to be the hydrazone. The co?tdensation p o d u c t with aniline, CZ4HZONZO3, melts at 136'. Benzylic pyruvafe is prepared diwctlg from its proximate consti- tuents; it is a liquid boiling at 103-104O (26 mm.), 107-108" (36 mm.), and at 207-208" under the ordinary pressure ; sp.gr. = 1.090 at 14O. The phenylhydrazone is a yellow substance melting at 150'. The co~tdensaticn product with aniline, CZJHZ2N2O3, melts at 173-174'; if kept, however, in the liquid in which it is formed, it is converted into a substance having a higher melting point and con- taining relatively more carbon. I n the prepaivation of benzylic pyruvate, a liquid is obtained, which, although closely resembling it, forms a compound with phenylhydra-ORGANIC CHEMISTRY. 87 zine containing a much larger percentage of carbon than the hydra- zone of the benzylic salt. Jx. W. Constitution of Tetric (a-Methyltetronic) acid. By LUDWIG WOLFF (Awzalcn, 189-5, 288, 1-37 ; compare Abstr., 1893, i, 689).- The author discusses the structure of tetric acid, which he regards CO - CHZ its having the constitution attributed to it by Michael, I >o; >O,a CHMe*CO YO*CH2 CH2 CO it is propofied to substitute thc name a-methyltehonic acid for tetric acid, it being a methyl derivative of tetronic acid, substance which will be deecyibed in a future communication.Pentic acid, therefore, will be called a-ethyltetronic acid. a-Methyltetronic acid (Demargay, Abstr., 1880,625) is obtained by brominating ethylic methylacetoacetate and heating the product for two hours at 180'; when heated with an aqueous solution of bnriuni hydroxide for 30 hours in a reflux apparatus, it yields glycollic and propionic acids, ethylketole being formed at the same time. E'thyZkeluEe, C2H5*C'O*CHP*OH, is obtained by heating a-methyl- tetronic acid (10 grams) with water (GO grams) in a sealed tube at, 200-210" ; it is a neutral, colourless oil which boils at 155-15tj0, and decomposes slightly under a pressure of 741 nim.It is readily soluble in wRter, alcohol, and ethei-, being precipitatcd from the aqueous solution by salts ; the substance reduces Fehlinp's solution and a silver solution, and is slowly decomposed by alkalis. Theyheuyl- hydrazoue crystallises from petroleum in yellowish prisms, and melts at 76-77' : the osazom crystailises in lustrous, yellow prisms, and melts a t 116". Carbonic anhydride and propionic acid are obtained on oxidising a-methyltetronic acid. >0, is obt.ained by treating the acid with boiling aniline, and pouring the product, into water ; i t crystallises in small, slender needles, and is resolved into its components by boiling, dilute hydrochloric acid.Its nitroso-derivative crystallises in yellow needles, and melts and evolves pas at 103-104". NH1'h.s- CH, CAfe*CO The nnilide of a-methyltetronic acid, U NHPh*yH- CH2 CHMeCO a-Methyl-&a ?iilidobz~tyrolactoiLe, >0, is formed when the anilide is reduced with sodium and amylic alcohol; it cqstallises from hot water in long needles, and melts at 92". The aqueous solution is neutral, and indifferent towards boiling dilute hydrochloric acid ; Fehling's solution is reduced by it when heated. The barium salt of the hydroxy-acid is obtained on treating the lactone with boiling aqueous barium hydroxide. The author has obtained the bromo-derivative of a-methjltetronic acid in long needles which sinter at 85' and melt a t 87-88"; the bromotetric acid prepared by Moscheles and Cornelius melted a t 75".The aqueous solntion is feebly acid, and after sonie time contains hydrobromic acid ; when heated a t loo', i t yields carbonic anhydride, diacehyl, and methyltetronic acid, a pungent oil which probably con- h 288 ABSTRACTS OF CHEMICAL PAPERS. sists of bromethylketole being formed at the saine time. Bromo- methyltetronic acid is immediately dissolved by ammonia and alkalis, and slowly by alkali carbonates, thc bromide of the metal being formed ; a concentrated Rqueous solution of sodium carbonate gives rise to methyl tetronic acid and cliacetyl. Methyltetronic acid is readily oxidised, yielding dirtcetyl, cnybonic anhydride, formic and propionic acids, and an oil which closely re- sembles ethvlketole.YO-CH, >0, is obtained by sus- NO* CNe *CO 2\Titr~60-~-~neth~ltetronic acid, pending a-methyltetronic acid in glacial acetic acid, cooling the liquid with ice, and submitting it to the action of a current of gas obtained from arsenious anhydride and nitric acid. On adding water to its solution in acetone, it crystallises out in minute prisms, aiid melts, evolving gas, at 130-13 1' ; i t is indift'erent towards cold water and hydrochloric acid, but yields nitrous acid and met hyltetroiiic acid with a small quantity of a-oximidopropionic acid when treated with the boiling agents. Cold aqueous ammonia gives rise to ammonium nitrite, methyltetronic acid, a-oximidopropionamide, and glycollic acid. a-OximidopropionyEgZycolZic acid, NOH:CMe*CO-O-CH,*COOH, is obtained when the gas from nitric acid and arsenious anhydride acts on methyltetronic acid in presence of water, and it is prepared ill the form of the sodium salt by dissolving the original substniice in concentrated aqueous sodium nitrite.It ci-ystallises from water in large, transparent prisms, and undergoes no chaiigct a t loo3: it melts a t 165O, slowly evolving gas, and is occasionally obtained in the form of needles containing water, which effloresce on exposure to air. The sodiwn salt cryfitallises in lustrous needles containing 1H,@ ; the siZz.ei* salt crystallises in needles which soon become prisms. The ncetyl derivative crysbllises from benzene ; i t sinters a t 1 0 2 O , and melts at 105'. Cold caustic soda, hydrochloric acid, and boiling water decompose a-oximidopropionylgl~collic acid, giving rise to a-oximidopropionic acid and glycollic acid ; the amide of thc former acid is produced by the action of ammonia, glycollic acid being formed ;it the same time.a-Oximidopropiouylgl~collic acid is obtained from nitrosomethyltartronic acid by treatins it with boiling solutions of sodium nitrite and sodium acetate, which, however, are without action when cold. The a i i h y d d e , which may have the constitution 0 C 0. CH, NGCMe - co>O, is obtained as a bye-product in preparing the acid from a-methyltetronic acid by means of sodium nitrite ; i t is an amor- phous, hygroscopic powder, which begins to decompose at iO", evolr- ing gas vigorously at 150'. It dissolves readily in alkalis and COA- centrated acids, and is converted into a-oximidopropionylglycollic acid on treatment with boiling watey.Dimethylvioluric acid and Dimethyldilituric acid. By RUDOLF ANDREASCH (Monatsh., 16, 773-788 ; compare Abstr., 1895, i, 336).-When dimethylvioluric acid is heated in a water bath with excess of potash, and the product acidified with acetic acid, carbonic anhydride, methylamine, and oximidomalonic acid are forined. If M. 0. F.ORGAN10 CHEMISTRY. 89 barium hydi-oxide solution be substitzted for the potash, carboiiic anhydride and oxinzidodinzethyZi,zaZoiza~~zide, HO*N:C( COmNHMe),, are obtained. The latter crystallises from water and from alcohol in needles, and melts a t 2%" (uncorr.). Xitrodimethylbarbiburic acid, if boiled with baryta water, or allowed to remain in contact with potash for several days, yields nitro&- methyZntalonamide, NO,*CH( COOH,)2, which crystallises from hot water in needles, nielts at 156" (uncorr.), and yields a barium salt, (CaH8X:104)2Ba + H,O, which crjstallises in drusy masses of prisms, a pofnssiiiin salt, which crystallises in white needles, and a copper salt, which is soluble in water, and crystallism in sky-blue octahedra.Nitro- dimethylmalonamide, when heated with hydrochloric acid in sealed tubes at l l O o , yields formic acid, carbonic anhydride, hydroxylamine, and methylamine. An aqueous solution is converted by chlorine and bromine into ch109'0iLit1.otliiizethylnzalonanzidc. and bro,,toiLitrodinzeth~L- mabonamide respectively ; the former crystallises in spear shaped needles and melts at 109" (uncorr.), the latter forms four-sided plates and melts a t 137-138' (uncorr.).These compounds do not yield salts, the halogen having become attached to the carhon atom bearing the nit1.o-group. Nitrodimethylbarbituric acid forms similarly consti- tuted compounds when timcated with chlorine water and bromine water respective1 y. Chlo~o~zitrodimetl~ylbal.hitu~ic acid, NO,*CCl: (CO*NMe),:CO, thus obtained, crystallises from chloroform in slender needles, and from alcohol in octahedra, and decomposes at 15G". Bromoizits.odi- methy lbarbitiiric acid, C6H6BrN305, closely resembles the corresponding chloro-compound, turns yellow a t 149", and melts partially a t 1 5 8 O . G. T. M. Methylethylhydantoin (Ethylpropiohydantoh) .By EDOUACD DUVILLlER (Bull. Soc. Chim., 1895, [3], 13, 487-490).-When Carl)- amide is heated with a-ethylamidopropionic acid, N HE t*C'HMe* C 0 OH, yHMe*NE t methylethylhydantoin (ethyllactylcarbamide), >CO, is GO--NH formed, the hydantoic acid appearing to condense a t once to the lactam. ,liletl~yEethyZhydnntoin crj-stallises in transparent, rhomboidal plates, and is very deliquescent ; it is stable towards boiling baryta water, so that the corresponding hydantoic acid cannot be formed by the action of this agent; the lactam is also formed instead of the acid by the action of potassium cyanate on ethylamidopropionic acid. It thus appears that this hydantoic acid is as unstable as the corresponding creatine, ;t ring compound being formed in both casea where an open chain compound might be expected.Thiohydantoi'n. By RUDOLF A ~ u i t e . 4 ~ ~ ~ (Monatsh., 1895, 16, 789-797 ; compare Abstr., 1888, 47) .-Thiohydantoinacetic acid, COOH*CHz<Co,NH> C:NH, is obtained on heating together at 1 0 5 O , ;t mixture of male'ic or fumaiaic acid (5 grams), thiocarbamide (3.3 JN. W. CH-S90 ABSTHACTS OF OHEMICAL PAPERS. grams), and water (4 c.c.). It is sparingly soluble in cold water, does not dissolve in alcohol, and ~ R S a powerful acid reaction (com- pare Tarnbach, Abstr., 1895, i, 13). When boiIed with barium hydpoxide, the acid is resolved into thiomalic acid, and probably cjanamide, although this was not identified, since from these two subst,ances thiohydantoinacetic acid can be directly synt,besised. On oxidation with barium chlorate in hydrochloric acid solution, thiohydanto'in- acetic acid yields carbamide and hydrothiosuccinic acid, COOH*CH,*CH( SH)*COOH.Diphen?llthiohydanto~~~acetic acid, obtained on heating a mixture of diphenylthiocarbamide and maleic acid for 14-2 hours at 140-144", crptallises from alcohol in yellowish, nodular masses, and melts a t 188' (compare Tambach, loc. cit.). G. T. N. Formation of 1 : 3 : 5-Trinitrobenzene and 1 : 4-Nitrophenol from Nitromalonic Aldehyde. By HENRY B. HILL and .TOSRPH TORRAY (Ber., 1895, 28, 2597-2599) .-The sodium derivative of nitromalonic aldehyde, N02*CNa(CH0)2, is formed whensodium nitrite acts on mucobromic acid. When its aqueous solution is treated with an equivalent quantity of hydrochloric acid and warmed, or simply allowed to remain, 1 : 3 : 5-trinitrobenzene and formic acid are formed.If its aqueous solution is treated with acetone (1 mol.), and soda is gradually added, 1 : 4-nitrophenol is formed. Preparation of Parethyltoluene and its Derivatives. BJ- GEORGE DEFRE?; (Rer., 1895, 28, 2648-2653).-The author has attempted to separate the mixture of ethyltolucnes, obtained by the action of ethylic chloride on toluene in the presence of alnmininni chloride, by a method similar to that used for the separation of the xylenes (Zeif. anal. Chew., 32, 243), but as it did not give good results he prepared parethyltoluene by Fittig's synthetical method, and obtained the following derivatives. Paret hy 1 toluenesuZphonic a cia, C6H3MeE t*S O,H + 1 4H,O, forms gI is- tening plates, melts a t 59-60', and is readily soluble in water. The bnrizm salt, ( C6H3&feEt*S03)2Ba + 2H20, crystallises from water in slender needles, and in the anhydrous form is insoluble in ether and in alcohol ; the sodiuna salt ci*ystallises with 1: H,O ; the sulphonic chloride is a yellowish, heavy oil, which solidifies when placed in a freezing mixture, and melts at 3' ; the sullphoiznmids is readily soluble in ether and in alcohol. PnrethzJltoluonitriZe, obtained by heating dry sodium ethylhluene- sulphonate with potassium cyanide, is a yellowish oil; i t begins to boil at 235O, but then rapidly undergoes decomposition, and cannot be hydrolysed by heating with concentrated hydrochloric acid at 200O.ChZoroparethyZtoZuei~e, obtained by chlorinating the hydrocarbon in the presence of iodine, is an oily liquid with an agreeable odour, and boils at 200" to 203' ; on further chlorination, it yields the dichloro.derivative, which boils a t 240-243". Orthobromcrparethyltolzlelze, obtained by the action of bromine on the C. F. B.ORGANIC CHEMISTRY. 9 1 hydrocarbon in presence of iodine, boils a t 22c)-222° (corr.), a t the same time undergoing slight decomposition ; the dibro?no-derivative [Me : E t : Br, = 1 : 4 : 2 ?] boils at 260-265O (uncorr.). Chloro~areth~ltolueiteszilphonic acid crystallises in glistening plates, which readily liquefy when 'exposed to the air. The barium salt crystallises with 4H20, the sodiziin salt is anhydrous, and the sdphonicl chloride is a yellow oil which does not become solid at -15'.Orthobromopareth~lfoliiei~esiLlplionic acid crystallises in thin plates, jields a ba&cm salt, (C6H,MeEtBr*S03),Ba + FiH,O, a sodium salt, C,H,MeEtBr*S03Na + €LO, an oily szilphonic chloride, and a sulplton- nruide which melts a t 143". J. J. S. Three Octochlorophenols. By XTIENN E BARRAL (Bztll. Sot. C'hiiri ., 1893, [3 3, 13, 490-492) .-Hexachlorophenol dichloride is the final product of the action of chlorine on phenol in presence of antimonic chloride, and exists in three modifications. The dark brown crystalline product is washed with dilute acid, and recrys- tnllised alternately from light petroleum and chloroform, yielding nltimately a white, crystalline mixture of the three isomerides, melting somewhat indefiuitely at 68-70". The separation is effected by hand, large and sufficiently characteristic crystals of the three varieties being obtained by slow evaporation of the ethereal solution in the cold. a-Hezachlorophenol dichloride, C,CI&, obtained in this manner is identical with that prepared by Benedikt and Schmidt by chlorinating pentachlorophenol in acetic acid solution, and it is also prepared by heating hexachlorophenol in sealed vessels a t above 210°, or a t R somewhat lower temperature in presence of bromine ; it crptallises in orthorhombic prisms, and melts at 103.5-104". ~-Hexachlompher~ol dichloridc crystallises in flat, orthorhombic prisms, and melts a t 89.5-90".It i; converted by fuming sulphuric acid into a hexac7Lloroquiizoize, which has a slight odour of camphor and melts a t $7.5-8S.5° ; this ketone is distinct from that of Zincke and Fuchs, and is converted by phosphorus pentachloride into hexa- chlorophenol and liexachlorobenzene dichlorides. yHexachloropheizo1 dichloride crystallises in monoclinic prisms, as broad as they are long, and melts at 88-89".The hexachloroph enol dichlorides are reduced to pentachloro- phenol by tin and hydrochloric acid, and are converted into t'he acetate of that substance by acetic anhydride ; they are decomposed a t temperatures somewhat above their melting points, into chlorine and products containing perchlorodioxyphenylene, but, on the whole, are much more stable than hexnchlorophenol, of which they are probably additive derivatives. JN. W. Formanilide and its Derivatives. By LUDWIG CLAISEN (Aiaitnleu, 1895, 287, 360--371).-0n a former occasion (Abstr., 1895, i, 62), the author traced an analogy between hydroxymethylene compounds, and formanilide, which he represented as hydroxymethy leneaniline, NPh:CH*OH, and this view has been accepted by Auwera (Abstr., 1895, ii, 41 ; compare also 1894, ii, 133) on the ground that in crjo-92 ABSTRACTS OF CHEMICAL PAPERS.scopic behnviour formyl deyivatires of primary bases differ fi-orn those of secondary bases. The author, however, no longer advocates his former conception of the constitution of formanilide on accouii t of the fact that, unlike the sodium derivatives of hydroxymethylenc compounds, sodium formauilide does not yield an alkyl ether when treated with alkylic iodides ; moreover, whilst hydroxymethylene compounds boil at a lower temperature than their alkyl ethers, formsnilide (h p.294") boils 82" higher than the ethyl ether. Detailed directions for preparing ethylforrnanilide (ethoxynaetlzyEeiw- aniline) from aniline and ethylic orthoformate are to be. found in the original paper (compare Cornstock and Clapp, Abstr., 1892, 708). I n preparing diphenylformamidine ())LethenyZb~.~anili?ze), there is 1 1 0 occasion to heat. aniline with ethylic orthofoririate in a sealed tube, as stated by Wichelhaus (BeT., 1869,2,116), the most coiivenient method being that adopted in preparing the foregaing substance, using the calculated quantities of material. When phenylhydrazine, dissolved in glacial acetic acid, is brought into contact with ethylic orthoformate at 0", formylphenylhydrazide and formazylhydride (Abstr., 1893, i, 83) are produced, the yield of the latter substance being larger than when ethylic formate is em- ploy ed.Sodium formanilide is conreniently prepared by heating in a reflux apparatus an ethereal solution of aniline containing sodium, and slowly adding the calculated amount of ethylic formate. Formjl- phenylhydrazide is obtained by heating sodiiim (23 grams), dissolved in alcohol (500 grams) with phenylhydrazine (108 grams) and ethylic formate (75 grams) for half an hour on the water bath ; one-third of the alcohol is distilled off, and the clear liquid obtained on pouring the residue on to melting ice is acidified with dilute acetic acid, wheii formylphenylhydrazide ( 108 grams) separates. Diazoperhaloyds. By ARTHUR R.HANTZSCH (Bey., 1895, 28, 275&2763).--Nine of the 10 theoretically possible diazopei-haloids RN2X, can readily be obtained (R = an aromatic radicle; X = a halo'id atom) ; attempts to prepare the trichloride have hitherto failed. These compounds are probably constituted according t o the diazoninm type NiNRX3 ; they closely resemble the alkali trihaloids, such as K13, CsBr3? HIM3, &c., of which, in the case of the cmhnri derivatives, eight of the 10 possible are known, the trichloride and the chlorodiiodide not having been described. The resemblance extends to the colouis : the diazotriiotlides are bluish-black, have a metallic lustre, and are almost opaque ; the diiodobromides are dark reddish-brown, the dibromiodides cherry-colonred, the tribromides orange, and the chlorobromiodides dark yellow ; the remaining com- pounds are less intensely coloured, the dicblorobromides being qale yellow.The colour is also influenced by the presence of substitutmg groups in the benzene nucleus. The cornpounds are unstable, but less explosive than the diazonium monohaloYds ; they are sparingly soluble in water, and generally a portion is decomposed; this property being most marked in the case of the two diiodides, the dibrom- and dichlor-iodides and the ch lorobromiodide are much more M. 0: F.ORQANIC C HEXISTRY. 93 stable. Alcohol dissolves them more readily, and less decomposition takes place; in ether, they scarcely dissolve, and undergo slow decomposition. Uiazoparachlorobenzene cyanide, by the action of bromine, is con- rerted, not into the additive compound C,H,Cl*NBr*NBr*CN, but into the tribromide, which is also formed from parachlorobenzene- diazonium chloride; this does not readily accord with the usual diazo-formula.All attempts, by varying the experimental condi- tions, to prepare structural isomerides, sach as PhNBr*NClI and Ph*y'C1 respectively, hare been uu- aiid I.N*Cl B r*N-I PhNC1-NIBr, or successful, it, is possible that the diazonium radicle N:NPh- is linketl to the trihalo'id group as a wholc rather than to any single atom ; this would be similar to the hydrogen-nitrogen Iinkiug in the irnide group of pyrazole, tetrazole, and probably azoimide. Attempts to eliminate selected haloid atoms from the above coiiipoundsy. particu- larly in the absence OF solvents which could cause dissociation, were unsuccessful. No pentahaloyds corresponding with CsX, could be isolated, b a t evidence of their probable existence is afforded by thc fact that ail the trihaloi'ds combine with Eromine, iodine, bromine iodide, and chlorine iodide and triiodicle to form dark colonred un- stable oils.The haloids may be employed in considerable excess without t h e benzene nucleus being attackcd ; this is in marked con- trast with aniline and its derivatives ; dimethylaniline rapidly attacks bromine water ; tri~nethylphenylammonium salts, like the diazoniurn salts, are without action ; this also favours the diazonium constitm- tion. Most of the dixzoiodides are unstable, and are possibly syn- derivatives. Diazomesitylene iodide, which will be described later, is exceptional in this respect, and, with alcoholic solution of iodine, yields mesityldiaxoniuiir t?*iiodide, C6H2Me3N,13, which crystallises iii dark brown needles with a blue i-eflex, a n d decomposes at about 70".Benzenediazoiiiunz chlorodiiodide, PhN,ClI,, .prepared from the di- azoninm chloride and alcoholic iodine solution in molecular proportion, crptallises in dark violet, lustrous needles, melts at 67", is stable in dry air, but is quant itatirely decomposed by water. The dichloriodide, PhN2C121, is formed by the action of alcohol on the preceding com- pound and subsequent precipitation with ether ; the action takes place in two stagm, a portion of the diiodide is resolved into iodo- benzene, nitrogen, and iodine chloi.ide, this then combines with the remaining diiodide forming iodine and the dichloriodide ; the latter is also formed from benzenediazonium chloride and chloi*iodide, itt is stable, crjstallises from alcohol in yellow plates, and melts a t 86-87".The bronzodiiodide, PhK2Br12, is prepared like the pre- ceding compouncls, and crystallises in lustrous, brownish-red needles. The dibronziodide, PhN2Bi;I, is obtained in n similar manner to the dichloro-derivative, and also from benzeiiediazoniuni tribromide and iodine ; i t forms brown crystals, and decomposes a t f7". The chloro- dibromide, PbN,CIBr,, prepared by the action of benzenediazonium chloride and bromine in chloroform solution, is a reddish-yellow, crystalline powder ; i t melts at 6l0, and is comparat,ively unstable. The Zwomodichloriclc, PhN,Bi.CI,, is formed by the action of chlorine Ph*r*Br94 ABSTRAOTS OF CEEMICAL PAPERS.on the tribromide in chloroform solution ; it crptallises from alcohol in pale yellow needles, melts at 63", and is imtnediately decomposed by water. The chloi*obronziodide, PhN,ClBrl, is formed from the diazoninm chloride or bromide by the action of bromine iodide and chlorine iodide respectively ; it is heposited in golden needles melting a t 80--81°. Parahromobenzenediazoniunz bronaodiiodide, C6H4Br*N2BrI,, can only be prepared a t about -E0, and forms brownish-red plates melting at about 79'. The dibromiodide, C6HpBr*N2Br2T, is obtained, to- gether with parabromiodobenzene, by heating the preceding com- pound with alcohol or glacial acetic acid, and also from the diszonium bromide and bromine iodide or iodine; it crystallises in brownish- yellow needles, melts and decomposes at 106-107°.The chloro- bromiodide, C6H4Br*N2C1BrI, is comparatively stable, and crystallises in golden needles melting a t 111-112'. The paranitrobenzenediazonium trihaloids are much less stable than the above compounds ; attempts to prepare the chlorodiiodide were unsuccessful, its even at very low temperatures nitrogen is evolved and paranitroiodobenzene is formed. Paranitrobenzenediazonium di- chloriodide, NO2.C6H4*NpCI2I, melts and decomposes a t 106'. The chlorobromiodide, No2*C6H4*N2C1BrI, forms yellow crystals, melts at 93", and, with alcohol, yields bromoparanitrobenzene. p-Laetylphenylhydrazide : Phenylhydraeine Citrate and Tartrate. By HESRY J.l?. DE VRIES (Ber., 1895,28,26ll--ZGl2).- p- Lactylphenylhydrazide, NHPh*NH*CO*CHMe*OH, is formed when phenjlhydrazine and lactic acid are heated together at 130-140' ; it forms white crystals, which melt at 114.5'. Phenylhydrazine citrate melts at 102'. PhenyEhydrazim d-tartrate probably has the formula, (N2H3Ph),C,H6o6 + 3H20, and turns brown in the air. Phen ylazocarboxylamide and Phenylazocarboxylic acid. By JOHAN N ES TH I EL E (Be?.. , 1895, 2 8, 2599-260 1 ) .- P hen y lazocarbox yl- amide, NPh:N*CONH2 (Widman, Abstr., 1895, i, 603), when it is formed in presence of water., crystallises with 2H20 as an orange- yellow powder that melts a t 84" ; i t readily loses its water by deli- quescence, or when recrystallised from organic solvents, and then forms red needles melting at 114".Its (mono-) potassiu?n derivative forms dark red plates. Potassium phenylazocarbozylate, NPh:N*COOK, is obtained by the action of potash on phenylazocarboxylamide, or by the oxidation of phenylsemicarbazide in alkaline solution ; it c r p t a l - lises in orange-red needles, and is decomposed by water. p-Pv~aphthyZazocarbolcyZa?nide is obtained, though much less easily than the phenyl compound, by the oxidation of /%naphthylsemicar- bazide ; it forms orange-red crystals, and melts a t 137-138'. J . B. T. A. H. C. F. B. Ketones from Propenyl Compounds. By Owo WALLACH and F. J. POKD (Ber., 1895, 28, 2714-2728).--1 anethoil is converted into the dibromide, and the latter treated with sodium methoxide, an oil is formed which contains the componnd, OMe*C6H4-C(OMe):CH&fe;ORQANIC DEEMISTRY.95 if the crude product of the action is distilled with steam, eth?yZ nnisyl ketone, OMe*CsHA*CO*CH,Me, is obtained ; this rnelts at 26-27', and boils a t 136-139' under 12 nim. pressure, at 265-270° under atmo- spheric pressure ; the osirne melts a t 74", the senticarbazoize a t 172-173". When oxidised with permanganate, the ketone yields anisic acid and a ketonic acid, OMe*C,H,*CO*COOH, which melts at 75", and is very soluble in water. When it is heated with strong sniphuric acid at. 200", some propionic acid is formed. Tsosafrole, CH2:O2:CsH3*CH:CHMe, and ethylisoaugenol, OMe*CsH3( OE t) CH:CHMe, behave in exactly the same way, the ketone formed always contain- ing the carhonjl group directly attached to the benzene ring.The ketone, CH2:O2:C,H,*CO*CH?Me, me1 ts a t 39", and boils a t 15.3-154' under 13 mm. pressure; the oxinzc nielts at 104". It is probably identical with the ketone obtained by Angeli (Abstr., 1892, 119S), and perhaps also with another obtained by Tonnies (Abstr., 1888, 264) from anetho'il nitrite. The ketone, OMe*C6H3(0Et)*CO*CH2Me, melts a t 62", and boils at 155' under 13 mm. pressure ; the owime melts at 114", the semicarbazone a t 1 7 5 O . When oxidised, it jields two acids, one sparingly soluble in water and melting a t 190°, the other (? ketonic) easily soluble, and melting at 64-45". The ketone is doubtless identical with that obtained by Hell and Portmann (Abstr., 1895, i, 657). C. F. B. Etherification and Hydrolysis.By RUDOLF WEGSCHEIDER ( B e y . , 1895, 28, 2%35-2536 ; compare Abstr., 1895, i, 499).-The author, in reply to Meyer (Ber., 1895, 28, 1798), maintains his former criticism of Iteyer's theory of the etherification of substituted ethereal carb- oxylates. He also criticises Briihl's treatment (Ber., 1895, 28, 1913) of the same question. Dinitrobenzoic acids. By Ftr. GBELL (Bey., 1895, 28, 2564- 2565).--2 : 5-Dinitrobenzoic acid can be obtained by oxidising with nitric acid at 140-130" the 2 : 5-dinitrotoluene obtained by Sand- meyer's reaction from 5-nitro-orthotoluidine. I n t h e same way, 2 : 3-dinitrobenzoic arid can be obtained from 2 : 3-dinitrotoluene, the latter being obtained when 8-acetotoluidide is nitrated, and the resulting 3-nitro-derivative treated with nitrous acid and cuprous oxide ; the acid melts a t 201°, the bariwn salt crystallises with 4H20.By EUGEA- BAMBEHGER (A.nnnZr?c, 1895, 288, 134-138 ; compare Abstr., 1893, i, 592).-1n ordep to establish the identity of the acid obtained by oxidising dihydronap h- tho1 with potassium permmganate (Eoc. cit.), isocoumarincarboxy lic acid was reduced with sodium amalgam, the product being identical with dihydroisocoumarincarboxylic acid, as already described. When isocoumarincarboxylic acid is treated during one hour with boiling, aqueous caustic soda, orthotoluic acid is produced, oxalic acid being formed a t the same time. Other ketonic acids undergo analo- gous decomposition ; thus pyruvic acid and phthalonic acid, A. H. C. F. B. Isocoumarincarboxylic acid.96 ABSTRACTS OF CHEMICAL PAPERS.COOH-C,H4*CO*COOH, yield oxalic acid when treated with boiling, aqueous soda, but benzoylformic acid does not behave in this way. The Red Isomeride of Indigotin; Derivatives of Isatin. 1 3 ~ EDWARD MCHUKCR and LEO MARCHLEW~KI (Bey., 1895, 28, 2525- 2531 ; compare Abstr., 1895, i, 288).-The three substances which liave been described as red isomerides of indigotin have been proved by the authors to be identical ; this identity is further shown by tthe fact that they all yield the same substance when treaked with zinc dust in presence of acetic anhydride and dehpdrated sodium acetate. This product crystallises in faintly pink, lustrous needles melting at 2043. M. 0. E’. It appears to be ncetylhzdileiiciu, by the reduction of pararnethylisatin chloride.I t crystallises i n chocolate-brown needles, and closely resembles indirubin. Isscrtiirmethylphenyl h ydruzoue, NMeP h*N:C< OH)>^, C-,H, - crystallises in orange needles melting at 172-17P; i t is strictly analogous to isatinphenylhydrazone, and ii; is, therefore, probable that both of these substances are true hydrazoiies, and not azo-compounds, since the ‘‘ mobile” hydrogen of the hydrazone is replaced by methyl in the methylhydrazone. lsntiizacetylmethylplisnylhydrazo~~e forms yellow needles melting a t 145’. _Tsnfi.12-P-naphth2jlhydrazolLe crystnl- lises i n dark yellow needles melting at 234’. Isatin readily reacts with orthophenylenediamine, isatohydropheu- aziTe, C14HSNR, being obtained; it is as yet doubtful whether this substance is a derivative of isatin or of pseudo-isatin.It crystallises in yellow needles which melt at 285--887’, and can be sublimed ; it is stable towards acids aiid alkalis, and is insoluble in the latter. The silcer salt is rz reddish-bromii powder. The acetyl deri?;ative melts at ‘ L O d O . lMetnchZorisatoh ydrophenaziiLe, CI4H&1N3, is prepared f porn meta- chlorisatin and orthophenylenediamine, and crystallises in sparingly soluble, yellow needles. Its silver salt is an orange coloured pre- cipitate. The acettjl compound melts at 215’. A. H. Reduction Products of Azo-compounds. By PAUL JACOBSON (Bey., 1895, 28, 2541-2558 ; compare abstr., 1895, i, 26).-The main object of the following research was to experimentally determine whether ortho- and meta-methylazobenzene and metazotoluene undergo the normal reaction when converted into benzidine derira- tives; all the three compounds were found to yield derivatives of paradiamidodiphenyl.Many of the substances described have already formed the subjects of patents. I. With W. LIscHKE.-Ort,homethylazobenzene is a red oil which boils a t 180-18lo (cori-.) under 20 mm. pressure. The hydraxo-ORGANIC CHEMISTRY. 97 cornpound melts a t 101'. 3-JIethyZbenxidiiie [Me : (KH2)2 = 3 : 4 : 4'1 is a syrup which conld not he obtained crystnllised. Its dibeuzylideite d e r i m t ive, C H P h K C ,H ,* c1 H,Me*N : C I3 P h , forms ye 1 1 o mi s h tablets melting a t 134". 4 : 4'-DiioJo-3-~i~etliyZ~~~7ie~~~Z, C6H,I*C6H3&~cI, is obtained by means of the diazo-reaction from methylbenzidine.It forms rosettes of needles, and melts a t 109'. When it is distilled with zinc dust, it yields metaphengltoluece, identical with the hydrocarbon which has been described by Adam (Abstr., 1888, 959). It follows from this, that methylbenzidine has been formed from orthomethylhydrazo- benzene in the normal manner. IT. With A. w. N~~h.~~~A.-~~etaine~hylazobenzene is usually pre- pared (German Patent, KO. 54,599) by the elimination of the amido- group from the condensation product formed from diazobenzene chloride and orthotoluidine; it may also be obtained by the con- densation of metanitrotolueiie with aniline in the presence of alkalis. It crystallises ill prisms, melts a t 18-19', boils at 175' (pressure = 19 mm.), and h a s t,he sp. gr. 1.065 at 20°/4'.Metanzethylli ydrazobemvie, NHPh*lu'HC6H4Me, crjstallises in yellow- ish needles, and melts at 59-61". The corresponding 2-methylbenzidine (4 : 4-dianaido-2-nzetl~yZdi- pkeizyl) cannot be obtained in the crystalline form. The hydmhlorid:. forms long needles. The diacetyl derivative crystallises in pointed prisms which do not melt when heated to 300'. The dibenzylidew derivative crystallises in groups of small needles and melts a t 11 1 -1 12'. OH.C6HA*C H: N*C6H4* C6H3Me*N:C H*C6H4*OH, crystallises i n slender prisms which me1 t indefinitely at about 160'. 4 : 4'-Diioao-'L-,iaethyZdipheil.yi forms arborescent crystals melting at 114-116'. 4 : 4'-Diliydroxy-2-methyldiphelz?/E crystallises in lustroue plates melting at 155-157'. When the diiodo-derivative is distilled with zinc dust, i t yields orthophenyltoluene, identical with the hydrocarbon described by Odd0 and Curatolo (Abstr,, 1895, i, 606).The formation of the benzidine compound in this case is, therefore, normal. 111. With 0. FAerA~.-Metazotolnene, together with some of its derivatives, has already bcen described by Buchka and Schachte- beck (Abstr., 1889, 701 ). The dibenzylidem dcrivative of the corresponding tolidbe, C12H,91e2(N:CHPh), [= 2 : 2' : 4 : 4'1, crys- tallises in stellate groups of light yellow tablets melting at 17%--173", '1% e diort hohydro2.y bemy liclene derivative melts a t 198-1 96'. This tolidine was then conirerted into the diiodo-derivative, and this. without compIete purification, distilled with zinc dust. The hydrocarbon produced is conrerted by oxidation into diphenic acid, and is therefore ortlioditolyl.The conversion of the Iiydrazc- compound into tolicline has, therefore, also proceeded normally in this case. IV. With K. MICHAELIS, and A. W. NANNJN~A.--~ : 4-Dirnethyltrzo- Oewene, CGH3Me2*N2Ph, prepared from metaxylidinc and nitrobenzene, boils a t %05--215" (pressure = 50 rnrn.), and lias the sp. gr. 1.071 a t The tliortl~ol~ ydrozy bewylideue derivative,98 ABSTRACTS OF CHEMICAL PAPERS. 20°/40. The h ~ d r a z o - c o ~ ~ ~ p o ~ c n d cvystallises in white needles melting at 77-79". 4 : 3'-Dimethylazobenzene, C,H,Jle-N,*C6H,Me, which has been prc- viously obtained by Ziiicke and Lawson (Abstr., 1886, 795), ma.y also be prepared from paratoluidine and metanitrotoluene. It crystallises in red needles melting at 55".The corresponding hydruzo-compo~c~icZ crystallises in colourless six-sided tablets and melts at 74'. A. H. Isomeride of Hydroxydiphenylethylamine. By HENRYK G. SODER~AIJM (Be,.., 1895, 28, 2522-2524).-The author has obtained, in the prepayation of hydroxydiphenylethylamine, an isomeric sub- stance which appears to be identical with t h e compound obtaiued by Erleumeyer by the condensation of benzaldehyde with glycocine (Abstr., 1895, i, 596), and by Polonowska by the reduction of benzile- monoxime (Abstr., 1888, 485). It melts at 1 2 9 O , and forms a Jryd~o- chloride which at first separates as an amorphous mass, but changes into slender needles. The plati~zochtoride, 2CI4H uNO,H,PtCl,, is pnhydrous, and melts at 213'.A. H. Stilbene Dibromides and Monobromostilbenes. By JOHANNES WISLICEN'US and FELIX SEELER (Ber., 1895,28, 2693-2703).-When stilbene is treated with bromine in carbon bisulphide solution, two, doubtless geometi*icxlly isomeric, dibromides are formed ; the less soluble a-compound melts at 237", the more soluble p-(iso)com- pound at 110-110.5°. The a-compound is always the main product, and so would appear to be the normal additive product of ordinary ~tilbene, but if that be so, i t is remarkable that increase of tempera- ture or of light intensity during the operation causes a large:. .amount of i t to be formed; as a rule the amount of the abnormal product is increased thereby. Either of the two dibromides under- goes a partial conversion into the otlier when heated.Both yield monobromostilbenes, when treated with alcoholic potash ; the a-com- pound yields an oil, the /?-compound crystals melting at 31". These bromosbilbenes both yield tolane when treated with alcoholic potash, but the crystallised compound does this very much more readily than the uthei., and heuce has the hydrogen and bromiue a toms in corresponding positions. From this the stereocheniicnl formuloe of the other compounds mentioned can be deduced. S tilbene S tilbene. dibromides. YPhBrH Ph$*H P h*C*H CPhBrH Phi I e- a. m. p. 237' symmetrical. (Meso-tartaric). YPhBrH Ph$*H HC-Ph CHBrPh Central- B. m. p. 110' symmetrical. (Racemic). 3 3 Monobromo- stil benes. Tolane. Ph-G-H Br* C*Ph e Oil. Central- \ Cph / CPh symmet,rical. I l l * Ph*f?H Ph*C*Br M.p. 31". Plane- symmetrica I.ORGAN10 CHEnIISTRT. 99 The dibromides are thus represented as derived from isomeric stilbenes ; the authors were, however, unable to obtain satisfactoiy evidence that stilberie does exist in two configurations. By HG. PREY (Ber., 1895, 28, 2514-2521).-Sodium decomposes ethylic oxalate into etliylic carbonate and carbouic oxide. When a solution of ethylic oxalate and bromobenzene in ether is treated with sodium, a mixture of hydrogen and carbonic oxide is evolved and triphenylcarbinol is formed together with benzoic acid. It is probable that the bromo- benzene is first converted into benzaldehyde or benzophenone by the carbonic oxide and hydrogen in presence of sodium, aud that the tri- phenylcarbinol is obtain-ed from this. The product actually contains n small amount of henzaldehyde, and both this substance and benzo- phenone yield tyiphenylcarbinol when they are mixed with bromo- benzene in etheteal solution aiid treated with sodium. The yield obtained from benzophenone is almost quanhitative.The author has attempted to prepare the corresponding derivative from acetone and methylic iodide, but without success, isopropylic alcohol being the chief product. Parabrornmiline, moreover, does not yield pararosaiiiline when treated with sodium rtnd ethylic oxalate, although nitrogen compounds of high melting point are formed. Alicyclic Derivatives of Naphthalene. By EUG EN BAM RERGER, and WILHELM LODTER. [with BERNHARD DEICKE! ( A n n u l e n , 1895,288, 74-1 33 ; compare Abstr., 1893, i, 591, and 1894, i, 419).-1 he paper coutains a detailed account of the preparation and properties of those derivatives which have been already described (Eoc.cit.), aiid the follow- ing facts (obtained in conj~ziictiou with B. Deicke) are also recorded, The hydrochloride and picrate of 2-dimet hylamido-3-hydroxy- tetrahydronaphthalene, CSHA<~ H,.CH-T.OH , melt at 180-181° nnd 182" i*espectively ; the awochloride crystallises in lustrous, yellow needles, and the pZatinochZoride forms orange-red leaflets. The methiodide crgstallises from water in long, lushi~ous prisms, and melts at 201", and the benzoate crystallises in aggregates of needles ; the latter has powerful toxic properties. The hydrochloride and picrate of 2-diethylamido-3-hydroxytetra- hJdronaphthalene (diethyltetrahydronaphtbylalkine) melt at 167- 1'10" and 170.5-1 71" respectively ; the a w o c h h - i d e crystallises in yellow leaflets or needles, and the pZatinochZoriiZe is orange-red.The 7Izetltiodide crjstallkes in white leaflets and melts at 151.5', and the beuzoate separates from alcohol in reddish-yellow, lustrous needles ; the latter forms a picrate which crystallises in yellow needles. The auwxhloride of 2-piperidyI-3-hydroxytetraliydronaplithalene crystallises in yellow leaflets, and the platinochloride separates from water in orange-red crystals. C. P. B. Formation of Triphenylcarbinol. A. H. CH,*$lH*NM e, Trimethyl-3-hydroxytetrahydronaphthylammonium chloride, CH,*QH*NMe,Cl csH4<c Hs' CH.0 H '100 ABSTRACTS OF CKEMIOAL PAPERS. forms crystals belonging to the monoclinic system : a : b : c = 1.0854 : 1 : 0.5081 ; /3 = 67' 43'.Precipitates similar to those formed Is!- choline are produced when the chloride is treated with common reagents for the detection of a!kalo'ids. The platinochloride crystal- lises in orange needles and melts a t 222-2235' ; tlie airrochloride separates from water in lustrous, golden-yellow leaflets, arid melts a t 132-154'. The p'crale crystallises in flat needles, and melts at 161-162". The hydrochloride of bishydroxytekrahydronaphthylamine, NH,(CloH,,*OH)zCl [NH : OH = 2 : 31, scparates from alcohol on adding ether in lustrous, white needles. The platinochloride, which is only sparingly soluble in cold water, crystallises in light-orango needles which melt and decompose at 835" ; the aurichloride crystallises in lustrous, yellow leaflets.The platinochloride of 2 : 3-hydroxytetrahydronaphthy:amine cq-s- tallises in reddish-yellow prisms, and the auyichloride forms needles. The picrate dissolves in hot water, and crystallises in needles. M. 0. F. Tetralkyldiamidoazonaphthalenes. By PAur, COH x (Monatsh., 1895, 16, 798-8806).-TetramethyZdiamido-a-azonuphthnlene is ob- tained on passing nitric oxide for two or three weeks through an alcoholic solution of a-dimethylnaphtbylaminc (compare Lippmann and E'leissner, Abstr., 1883, 55, 184, 868, 1100). It separates from alcohol, in which i t is only'sparingly soluble, in brownish-red, dichroic crystals, sinters a t 140', and melts at 145' ; it. yields a yellowish-brcwn cry st d l i ti e picraf e, C2rHz4N4,2CsH2( N02),*OH, which is a1 most in- soluble in boiling orgmic solvents, and, on reduction with stannous chloride in hydrochloric acid solution, forms paradimethylamido- napbthylamine (compare Friedlander and Welmana, Abstr., 1189, 150).Tetreth yldia?iiido-2-azoiLaphf halcnc, obtained in a similar manner to that employed in preparing the tetramethyl compound, crystallises i n reddish-yellow, rhombic plates, gives, with hgdrochloric acid, a blue coloration, which.is destroyed on the addition of water, and melts a t 143' to a reddish-brown liquid ; it yields a p k r a t e , C2,H&N,,2CsH,( KO?)s*OH: which crrstallises in reddish-brown necdles, is spariiigly dissolved by ordinary solvents, and melts and decomposes a t 200'. Dipropyl-a-naplithylnmiiie, C16H21N, obtained on heating a mixtiire of a-naphthylamine, potash so111 tion, and normal propylic iodide under pressure at 180', boils at 300', has a specific gravity of 0.9935 at 20°, yields a hydrochloride, C16H21N,HCI,H20, which crystallises in white kedles, a hyd&dide, C16H21N,HI, which crystallises in yellow, felted needles, and a yellow platinocldoride, (C,,H21~)2,H2PtC16, which darkens a t 160", and melts and decomposes at 212'.No definite azo-compound could be obtained by the action of nitric oxide on d iproyyl- a-nap h t hy lami 11 e. G. T. M.ORGANIC CHEMISTRY. 101 Terpenes and Ethereal Oils. Phellandrene. By OTTO WAL- IACH and AD. HEIWIG (Annctlen, 189.3, 287, 371-3843 compare Abstr., 1887, 965 ; 1888, 1204).-The result of the author's investi- gation shows that reduction of phellandrene nitrite gives rise to optically active tetrahydrocxrvone, tetrahydrocarveole, and tetra- hydrocarvylamine, the inactive modifications of which have been already described (Abstr., 1894, i, 44) as arising from carvenone (Abstr., 1895, i, 622), on reducing it with sodium and alcohol ; on pre- paring racemic mixtures of the compounds from d- and I-phellandrene, inactive tetmhydro-derivatives of the carvone series are obtained.Phellandrene nitrite, which melts at 105", is prepared in the fol- lowing manner ; 100 grams of hydrocarbon, rich in phellandrene, are placed in a beaker surrounded by a freezing mixture, along with 400 grams of petroleum, and covered with dilute salphuric acid, prepared by mixing 37 grams of the coiiceritrated acid with twice its volume of water ; 230 grams of a 44 per cent.solution of sodium nitrite is then slowly added, the temperature being maintained below 4", and the liquid gently stirred from time to time. Eucalyptus oil was em- ployed as the source of I-phellandrene, bitter fennel oil being used when derivatives of d-phellandrene were required. When phellandrene nitrite is treated with alcoholic sodium ethoxide, i t becomes red, heat being generated and nitrous oxide liberated ; in this way, npale yellow oil is obtained, which boils a t 134-138', aud has a penetrating odour ; it is identical with the " nitrophellandrene " describefi by Pesci (Abstr., 1886, 1038). On reducing phellandrene nitrite, or the foregoing compound dissolved in absolute alcohol, with sodium, the ketone, CIOHIBO, the alcohol CloH200, and the base CloH19*W€Z, are obtaiiied.The ketone boils a t 90-100" under a pressure of 15 mm., and yields a dextrorotatory oxime, which crystallises in needles, a i d melts a t 97-98' ; the sernicarbazo?ae melts a t 185-187'. The alcohol (tetrahydrocarveole) is obtained on reducing the ketone wit.11 sodium and alcohol; it boils at 100-104°under a pressure of 12 mm. The base (tetrnhydl.ocarv?lIamine, Abstr., 1894, i, 44) boils at 210-212', and absorbs carbonic anhydride. The hydrochloride melts at 199--204", and the acefyl derivative :tt 158-159" ; the carbanride and phenylcarbamide melt at 201-203O and 185-186' respectively. When sodium nitrite is added to a feebly acid solution of the hydro- chloride, the alcohol is produced, and this substance, on oxidatioxi, yields the ketone.The authors discuss the constitution of phellnndrene. Pinole. M. 0. F. By Om0 WALLACH (Bey., 1895, 28, 2708--2713).--The anthor has modified the formula. he previously gave to pinole (Abstr., C H,* C H: CMe , CH as the most 1895, i, 59), and now regards CEI------CH2- probable, although it does not satisfactorily explain all the reactions ; in deducing it, regard was had to the fact that terpineole appears to have an hydroxyl group in a side chain. If pinole glycol is prepared from pirole by direct oxidation, a,nd also by means of the dibromide of the latter, the properties of the two samples are not qcite identical. VOJI. LXK i. i / 'CMez-- 0'102 ABSTRAGTS OF OHEMICAL PAPERS.The ketone, CIOHIBO, prepayed by reducing pinole tribromide (loc. cit.) in acid solution, has been obtained pure by means of its semicsrbazone; it boils a t 214-217'; a t 20' its sp. gr. = 0.916, and index of refraction ?zD = 1.46603; the semicarbazone melts a t 158"; the oxime boils a t 150" under 15 mm. pressure, and can be reduced to a base C10Hl,*NH2, the hydrochloride of which can be transformed into a carbamide, CloH17.NH*CO*NH2, melting a t 188O. The ketone probably contains one ethylene linking, possibly in a'side chain in which it is probable that the oxygen atom also is contained. The alcohol, CloH180, obtained by reducing the pure ketone, boils at 108" under 15 mm. pressure, has sp. gr. = 0.913, and index of refrac- tion ?aD = 1.47292 at 18". If pinole tribromide is treated with silver acetate in the cold, a compound, CloHl,Br,O*OAc is formed ; if heat is employed, an acetate containing no bromine is obtained, the semicarb- azoiie of which melts a t 177-178". By OTTO WALLACH (Ber., 1895, 28, 2703-2707) .-When dihydrocarvone is oxidised, two ketones are formed, in addition to various acids, including oxalic acid and a a acid that melts a t 205-204", and contains 59.43 and 8-33 per cent. of carbon and hydrogen respectively.The ketone formed i n larger quantity melts at 115-120°, and boils a t about 200" under 100 mm. pressure; it is a ketoglycol, CIOH1803, the oxime of which, C,,H,,O,:NOH, melts at 202", and the seinicarbazone a t 187"; when boiled for a long time with dilute sulphuric acid, it yields a ketone, boiling at 220', the semicarbarone of which melts a t 206'. The second of the two original ketones boils at about 130" under 10 mm.pressure, and solidifies in a freezing mixture ; i t is a diketone, C9HI4O2 ; its oxime and sernicarbazone melt at 195' and 203-204' respectively ; it can be obtained from the ketoglycol by further oxidation. By ARNOLD HESS (Bey., 1895, 28, 2687- 2693).-Pure camphoronic acid, G9H1406, melts at 148-150" when it is placed i n a bath at 136O, and the latter rapidly heated. When it is slowly heated, starting from the ordinary temperature, it is con- verted for the most part into the anhydride. It yields a triethylic, together with the diethylic, salt when it8 solution in absolnte alcohol is saturated with gaseous hydrogen chloride ; it boils at 295-300'.When the diethylic salt is treated with alcoholic ammonia, it yields ammonium ethylic camphoronamate, melting a t 144--145O; this can also be obtained by the action of ammonia on eth ylic anhydrocamphoronate, 0: C20 I:C6H,l*COOEt. When boiled with aqueous alkalis, it yields camphoronimic acid, NH:C2O2:C6Hl,-COOH, melting at 210". When the above-mentioned diethylic salt is heated at 120-130' with alcoholic ammonia, OF when a benzene solution of anhydrocamphoronic acid is saturated with ammonia and then heated a t 140°, ammonium cumphoronimate, NH:CzO2:C6Hll-COONH~, melting at 175O, is formed ; this only loses half of its nitrogen when boiled with aqueous alkalis. By heating C. F. B. Oxidation Products of Dihydrocarvone. C. F. B. Camphoronic acid.NH2*CO0C6Hl1 (CO OE t)*CO ONHI,ORGANIC OHEMISTRY. 103 triethylic camphoronate with alcoholic ammonia a t 1 7O-l9OG, a €ew crystals, melting a.t 210-218', were obtained ; these were possibly camphoronimic amide, NH:C20,:C6Hl ,*C 0 NH,. C. F. B. Compounds from Lichens. Atranoric acid and Substances accompanying it. By WIramM ZOPF (Annalen, 1895,288,38-74 ; compare Abstr., 1895, i, 297).-Atranoric acid is the substance first isolated from Lecaitora a t m (Hudson) by Paternb and Oglialoro (this Journal, 1877, ii, 986) ; its presence in Cladonia miigiforniis (Schaerer) and Stereocadon ceszccianum (Pers.) has been since observed by Paternb, and its existence in the dissimilar groups, to which the first-named lichen and the last two belong, has led the author to conduct a systematic search for atranoric acid among 33 different varieties. The investigation has revealed the presence of this acid in the lichens Stereocaulon nlpinum (Laurel.), S.coyalloicles (Fries), X. incrustatum (Florke), S. denudaturn (Florke), xnr. geiauinum (Fries), 8. fonzentosum (Fries), X. pileaticm (Acharins). S. condensatirm (Hoffmannj, S. paschale (L. and Fries), S. virgatum (Ach.), forina pTiinaria (Wainio), 8. Tarnulosum (Ach.), Physcicc cwia (Hoff mann), 2'. pulvemlenta (Schreber), var. P-pityrett (Ach.), P. endo- coccina (Korber), P. fenella (Ach.), P. aipolia (Ach.), Anaptychia ciliaris (L.) , A . speciosa (Wulf), Parmelin encausta (Sommerfelt), P. pertusa (Schrk.), Parmeliopsis hypempta (Ach, and Nyl.), Hceiircc- tomma coccineuni (Dickson) , Placodiwna saxicol m a (Poll.), and P.i)ielnnaspis (Ach. and Fries), in addition t o those already mentioned. The cortex of the thallus i s stained yellow by alkalis in the case of those species which contain an appreciable amount of atranoric acid, the coloration being very feeble when the acid is present in small quantity; the test, however, is not trustworthy, as a yellow stain with alkalis may arise from the presence of evernic 01' thamnolic acids. The lichens Ecenzatoninta centosum ( L.), Placodiunt o.adiosurn (Hoffmann), Cladonia comztta (Ach.), C. gracilis (L.) f o r a a chorduIis (Florke), c'. g., formn mpem, C. ntacilenta (Ehrb.), C. furcatn (Hudson) forma polyphylln (Florke), and C. spmmosa (Hoffmann), do not con- tain atranoric acid, and Placodizmz crassum (Hudson), ider?tical with Psoyoma Crassuwi, caT.cwspitosuni (Schaerer), contains oniy n trace of it. Atranoric acid, Cl9Hl6O8, has been already described by Paternb and Oglialoro (loc. cit.) ; it separates from chlorofoi-m in crystals several millimetres in length, and melts a t 195-197'. The crystals belong to the rhorubic system ; a : b : c = 0.7773 : I : 1.2808. A h - noric acid yields with alkalis R yellow solution, from which it is pre- cipitated by carbonic anhydride ; a yellow coloration is developed on dissolving the substance iri conceiitrated sulphuric acid, and the alco- holic solution becomes purple-red with ferric chloride. Hcematonmic acid, Cll€T1205, is obtained by heating atranoric acid (1 gram) with absolute alcohol (40 c.c.) in a sealed tube at 150' for oue hour; it crystallises from dilute dcohol in snow-white, silky needles, and melts st 113--114".It is exceedingly soluble in hot alcohol, and also dissolves in cold ethei-, chloroform, aud benzene, whilst cold alcohol and light petroleum dissolve it b u t sparingly ; the substance dissolves in alkalis and alkali carbonates, formicg a yellow104 ABSTRACTS OF CHEMICAL PAPERS. solution, from which it is precipitated by carbonic anhydride, and the alcoholic solution develops a purple-brown coloration with ferric chloride. When an alcoholic solution of atrnnoric acid is boiled for mahy hours in a reflux apparatus, h3ernatommic acid is produced ; it is, therefore, undesirable to employ boiling alcohol in recrystallising atranoric acid, and prolonged treatment of the lichens with boiling alcohol is to be avoided.Hsmatommic acid has been isolated from the lichens Hmntatomma coccineurn and Physcia ccesia. Hematonzmenic acid, C21H22010, is obtained by heating atranoric acid (9.5 grams) with methylio alcohol (20 c.c.) in a sealed tube at 150' for one hour ; it crystallises from a mixture of methylic alcohol and chloroform in thread-li ke aggregates of colouyless needles, and melts a t 146-14'i0. The solution in alkalis and alkali carbonates is yellowish-green, and the acid is precipitated by carbonic anhydride. Omrnatic acid is formed when atranoric acid is heated with propylic alcohol in a sealed tube at 150" for one hour; it melts at 75', and dissolves in alkalis and alkali carbonat'es, forming a Fellow solution.In addition to the lichens already mentioned (Abstr., 1895, i, 298), Lecanom (Zeora) scrdida, Hamatornma C O C C ~ ~ L ~ ~ L ~ L , and Placodlzcm saxicolzim contain zeorin, which crys tallises from chloroform or abso- lute alcohol in hexagonal double pyramids ; it melts a t 247-252", and is insoluble in hot alkalis. When treated with boiling alcohol and hydrochloric acid, it yields zeorinii~, which c~ystal lises in colour- less, lustrous leaflets, and melts at 182--284O; tbis is insoluble in alkalis, and dissolves in concentrated sulp huric acid with develop- ment of a yellow coloration. Usnic acid has been isolatsd from Hcematonzmn coccinezim and H. ventosuin, whilst the lichens i3te~eocaulorL comlloades, S. incrustaizcm, S.' vesuvianicin, and S.denudatum contain psoromic acid. Placodiit is a copper-red substance obtained from Placodiurn naeka- naspis (Ach. and Fries), identical with 1'. iiijlatunz (Korber) ; it crystallises from absolute alcohol in thin, pleochro'ic plates, and melts and decomposes at 245". It dissolves with difficulty in ether and chloroform, and is nearly insoluble i n benzene ; the solut.ion in caustic soda is violet-brown, and concentrated nitric acid dissolves it with development of a yellow coloration. S;'tc;.eocaulic acid is isolated from Stereocuulon, akinzcm and Lepra chlorina, and crystallises from alcohol in white needles melting at 200-201"; it d'ssolves with difficulty in alcohol, ether, benzene? and chloroform, and carbonic anhydride does not precipitate the acid from its solution in sodium carboilate, which is yellow-.The alco- holic solution develops a violet coloration with ferric chloride. 31. 0. F. Nitro-derivatives of Pyridine. Bg HUGO WEIDEL and ERNST MURMANN (Moizatsh., 1895, 16, 749--759).-The authors obtain pyridine-p-sulphonic acid, in the exceptionally high yield of from 45 to 65 per cent., by the sulphonation of pyridine in presence of anhydrous aluminium sulphate with 33 per cent. anhj-dro-sulphuric acid at 330-350'. The sulphonic acid is first converted into P-hydroxg- pyridine (m. p. lag"), nd asubsequently into its acetyl derivative,ORGANIC CHEMISTRY. 105 and the latter is nitrated by the addition of nitric acid to an ice-cold solution in acetic anhydride ; the action is then completed a t the ordi- nary temperature, the acetic anhydride removed by distillation under diminished pressure, and the residue hydrolysed with sodium hydr- oxide. OD adding hydrochloric acid to the product, a precipitate i s obtained which, ou exhaustion with boiling water, leave9 an insoluhle nitro-/3-hydrozypyridine. This crystal lises f roin alco h ol i 11 du 11, yello \v needles, and melts and decomposes at 295-298" (uncorr.).The aqneoiis solution, on exhaustion with ether, yields a ~iiaitro-/3-hytl?.ox2/pyridilLc! which crystallises from the ethereal solution in dull, yellow needles, and melts a t 133" (uncorr.). A second ?litl.o-P-h!/d,.o,rypyridine crystal- liaes from the aqueous solution in pale, lemon-yellow plates, aiid melts at 210-211° (uncorr.). G. 1'. 31. Direct Introduction of Hydroxyl-groups into Hydroxy - quinolines.By JULIUS DIAMANT (Afonat.sh., 1895, 16, 760-772).- When 1-hydroxyquinoline is heated a t 380°, with 10 times its weight of caustic soda and a little water, hydrogen escapes, and 1 : 2'-dL'- 7/ydroz?lqz~i72oZine, C9HiN02, is formed ; this crystall ises from water i n scales, melts with partial decomposition and sublimation at. a tempera- ture above 260°, andgives a dirty green coloration with ferric chlo- ride. The hydrochloride, CgH7N02, HCl+ H,O, crystallises in yellow- ish-white needles 01' scales, and is very unstable. The acefyl dprimtice, CgHsNOaAc, foibms crystdline scales, and melts :it %44+-247". On oxidation with potassium permnnganate in alkaline solution, the dihydroxyquinoline yields 6-hydroxyquinolinic acid, thus showing that the second hydroxgl-group is in the 2' position. Trih-jdroxyquinoline, C,H,NO,[(OH), = 1 : 2' : ?I, obtained on further heating the above-described dihydroxyquinoline with excess of caustic soda at 380°, crystallises in long, colourless needles ; it is almost insoluble in ordinary solvents, but dissolves i l l borax solution and in alkalis, has an intensely sweet taste, and gives with ferric chloride a dirty green solution, which is turned brown by sodium carbonate.Trihydroxyyuinoline may also be obhined by long-con- tinned heating of hydroxyquinoline with excess of potash. G. T. M. Formation of Thiazole Derivatives from Uric acid. By HUG( I WEIEEL and LADISLAUS NIKIIILOWJCZ (Monatsh., 1895,16, 721-748).- When uric acid (2.5 grams) and ammonium hydrosulphide (15 C.C.of a solution obhained by adding 1 vol. of commercial ammonia to 2 vols. previously saturated with hydrogen sulphide) are heated together for four hours at 1 8 5 O , 3-amidourncyl Zhydrosulphide, is formed. It crystallises from dilute acetic acid and from strong hydrochloric acid in slender needles, which do not melt a t 300°, forms an unstable anhydrous ammonia compound having the composi- tion C4H5N,SO2,NH,, and on the addition of bromine yields uranil, iso- barbituric acid, and other substances. On heating with a large excess i 2106 ABSTRACTS OF CHEMICAL PAPERS. oE acetic anhydride? amidouracrl hydrosulphide yields the crystalli tie metyl derivative, CAH7N3SO3, which is soluble in water, amylic alcohol and acetic acid, with partial decomposition, and melts and deuoni- poses a t a hemperatwe above 300'.On treatment with water, O Y better, with a dilute alkaline solution, the acetyi compound jields the 1i ,.eide of p-met h y 1 - f i - o ~ y th iazole- a-ca r b ox y 1 ic acid, which crystallises in felted masses of small needles, is soluble i n water containing acids and alkalis, dissolves sparingly in alcohol and ethylic acetate, and gives the following salts. An ammonium salt, C,H,N,SO,,RH,*OH, crystallising in hair-like needles ; a sodium s d t , with 2H20, crystallising in colourless needles ; a bariiLrn salt, and an anhydrous crystalline silrer salt, C6H,N3S02Ag. When the ureide 01' its acetyl derivative is boiled with acetic anhydride and sodium acetate until no more carbonic anhydride escapes, and the excess of acetic anhydride is distilled off, the residue contains P-acefyl- nmido-~L-nieth2/lthintole-~-ca~.boxylonit~le.This is insoluble in cold chloroform, but dissolves in the boiling solvent, from which it crystallises on cooling in long needles, and, when quickly heated, me1 t s at 280--285O, undergoing partial sublimation. The residue also occasionally contains the p-acety1a.mido-pL-methylthiazo1e-u-cn,.- Aoxylacetylanzide, which dissolves in cold chloroform and in water, melts at 176-178" (uncorr.), and, on further treatment with acetic acid and sodium acetate, gives the nitrile C,H,N3S0. Each of these products from the residue is converted by dilute hydrochloric acid inbo /3-amido- p- meth y 1 t hiazol e-a- car boxy 1 anzide, C5H,N3S 0 + d H 2 0 , which crystallises in yellowish-white, monoclinic plates, [a : b : c = 2.783 : 1 : 1.2781, is only sparingly soluble in cold watey, melts with decomposition a t a temperature above 300°, and, on fusion with potassium hydroxide a t 260-280", yields a crystalline mixture from which two substances were isolated, one soluble in alcohol and the other insoluble.The insoluble substance, formed only in small quantity, It is ,(3-am~do-~-~~aethy~t~~iazo~e-u-cu~boxy1ac acid, CMe< S *g*NH, 'N-C*COOH' crvstallises from water, in which it is fairlv soluble, in scales. and dgcomposes a t '200". The soluble portion i9' apparently the hydro- c h l o d e of /3-amido-p-methylthiazole, CMeGN.8 ~ , which is S *C*NH2 readily dissolved by water, the solution giving an intense cherry-red coloration with ferric chloride, crystallises in scales, and decomposes at 250'. Azimido-~~-nzet~Lylthiazole-a-ca~bolcylic acid, which crystallises iu yellow scales and decomposes a t 270-280", is obtained on dissolving &amidomethyIthiazolecarboxylamide in hydrochloric acid, adding the requisite quantity of potassium nitrite,ORGAN10 OEEMISTRY.107 bailing tlie solution, evaporating in a vacuum, and finally extracting \v i th alcohol. G.. T. M. Tetrazole Derivatives. By JOHANN vs THIELE arid HARRY 1wi,il: (,hza/eu, 1895, 287, 233-265 ; compare Abstr., 1892, 1295, and 159:3, i, 440).--AmidotetrazoZe is the name by which the authors now refer to arnidotetrazotic acid (Zoc. cit.), which has the constitution, N-x I I The cyanate is obtained by adding potassium cyanate N*NH to an 9.queous solution of the hydrochloride ; it melts above 2.50G, aiid dissolves in dilute hydrochloric acid with liberation of carbonic.anhydride, having the odour of cysnic acid. Boiling water decom- poses the cyanate, giving rise to carbonic anhydride, ammonia, and amidotetrazole ; an alcoholic solution of aniline yields phenyl- carbamide. ZZei~~oyZaPnidotetra=ole dissolves readily in alkalis, and melts and deccmposes above 250” ; the ncetyl derivative crystallises in white leaflets melting a t 2Gg0, and has a strongly acidic reaction. k’uming hydrochloric acid does not attack amidotetrazole at 160-170”, but at 200--210° carbonic anhydride, ammonia, nitrogen, and hy- drazinc are formed, the last-named being produced in theoretical quantity.In preparing beiizylidenetetrazylhydmzine (Zoc. cit.), an improved yield is obtained by regulating the quantity of hydrochloric acid in such a manner that at the conclusion of the operation excess of this agent is a minimum. I I , crystallises froin glacial acetic acid, and sinters at 140-150°, melting at 192”; it is strongly acidic, and does not develop a red coloration with ferric chloride. Acetophenonetetrnzylhydruzone is obtained fi*om aqueous tetrazylhydrazine hydrochloride and alcoholic acetophenone ; it melts at 235O, and dissolves readily in alkali carbonates. Acetow- tet,.ctzyZl~yd/.cczo?~e is prepared from tetrazylhydrazine hydrochloride and acetone in presence of sodium acetate ; it crystallises from water.. and melts at. 181.5O.Tetrnzylsenzicarbazide is formed on mixiug warm, aqueous solutions of potassium cyansta and tetrazylhydraziiie hydrochloride; it melts a t 211’ if slowly heated, a t 218’ when the temperature rises rapidly. The semicarbazide is acidic and stionglly reducing, and is sparingly soluble in cold water ; an alkaline solution of potassium permanganate oxidises i t to tetrazolazocarboxylic acid, of which the sodium derivative was precipitated, ammonia being liberated at the same time. Tetrazylazoimide (diazotetrnzolei~t~ide), I I >CON< I I , is obtained by adding 5 C.C. of concentrated hydrochloric acid mixed with ice to an ice-cold solution of tetrazylhydrazine (2.3 grams) and sodium nitrite (2 grams); it crystallises from benzene in beautiful white needles.When rubbed slightly, or on heating gently, it explodes with greater violence than silver azoimide ; it dissolves readily in water and acetone, but is insoluble in petroleum or ether, >C*NH,. N--N NH*N l’r.iacetyZtet,.azllZhydrnzine, NAc2*NAc*C< N-N N N*NH N108 ABSTRAOTS OF CHEMICAL PAPERS. and yields azoiniide when treated for seveml hours with boiling coii- centrated potash. The silver derivative is insoluble in cold, dilute. nitric acid, and explodes violently in the moist state : the derivative is a, white powder, obtained on passing dry ammonia into a solution of tetrazylazoimide in benzene, and does not explode with greater violence than gunpowder. The ammonium salt is very solnble in water and methylic alcohol, but dissolves less readily in benzene.Fuming nitric acid decomposes tetrazylhydraz ine at 1 W , giving rise to hydrazine, carbonic anhydride, and nitrogen. Dihyd,.obenzyZidenetetraz~lhydl.a~int: is obtained by reducing beii- zylidenetetrazylhydrazine with sodium amdgnm ; it crystallises f t v n i alcohol, and melts and decomposes at 187-191'. The sodium derivn- tive is colourless, and crystallises from dilute alcohol. The dihydro- derivative differs from benzglidenetetrazylhydrnzine in dissolving i i i dilute mineral acids, and forming a sdphate which is sparingly solnl~lc in cold water; it is, moreover, readily osidised by mercuric oxide or an arnmoiiiacal silver solution, whilst these agents attack benzylideiie- tetrazylhydrazine slowly when heated. When the dihydro-compound is treated with boiling hydrochloric o r sulphuric acid, a small quati- tity of benzaldehyde is formed, but a t 1603 hydrochloric acid gives rise to benzylidene chloride and hydrazine.Acetonetetrazylhydrazoiie is indifferent towards sodium amalgam. When sodium diazotetrazolate (Zoc. cit.) is reduced with alcohol, tetrazole is produced ; this crystallises from ethylic acetate in aggre- gates of needles or leaflets, and melts at 156' (compare Bladin, Abstr., 1892, 1009). On heating tet,razole with hydrochloric acid for threc. hours at 200°, animonium chloride is formed, but no hydrazine ; it is completely decomposed by hot, concentrated sulphuiic acid, yielding nitrogen and carbonic oxide. The sodium derivative of tetrazole contains lH20, and crystallises in thin prisms, which dissolve very readily in water.The barium derivative contains 3iH20, and crys- tallises in large, transparent prisms, which become nearly anhydroni; in the exsiccator ; it belongs to the rhombic system, and has a : b : c = .0*5689 : 1 : 0.7217. The conductivity constants of tetrazole, of thr. sodium derivative, and of amidotetrazole have been determined. N-N NMe*N 1.1 :is obtained by heat- MethylamidonzethlJZtetl.azole, NHilIe*C< ing anhydrous amidotetrazole (1 0 grams) with methylic iodide for three hours at 160-165" ; it crystallises from ethylic acetate in leaflets, and begins to decompose at 80'. The substance is very hygroscopic, m d its solution is strongly alkaline. The hydrochloride crys tallises from alcohol in white needles, and melts and decomposes at 241"; the picrate melts and decomposes a t 20.3".The awochloride cry stallises from water in large plates, and melts at 164"; the platinoddoridti crystallises from alcohol in golden-yellow needles, and from water in large prisms, melting at 200". The nifrosamine forms yellow needles, and yields nitrous acid under the influence of dilute mineral acids, nitrogen being evolved on treating it with potash. Methylamidotetruzole crystallises from water in white needles, and me1t.s at 218-220" ; the aqueous solution is neutid. Eth$laiii/&-ORGANIC CEEMISTRP. 109 ethyltetyazole hydrochloride is very soluble in water and alcoliol, and forms white needles melting a t 232-233'. a-BemyZamidotetrmole is obtained by boiling benzylic chloride ( 2 mols.) with amidotetrazole (2 mols.), sodium carbonate (1 mol.), water, and alcohol, until the odour of benzjlic chloride is no longer perceptible ; it melts a t 191-192", and is neutral.P-Be?,z!ylarzlido- tetrazole, CH2Ph.NH*C< I I , is formed on heating amidotetrazole (10 grams) with benzylic chloride (40 grams), caustic potash (50 grams), and dilute alcohol, for six hours ; it melt,s a t 181", and dissolves in alkalis. N-- N NH*N Benzy~a?nidobenzyZtetrazole, N--- N:y N*NCHzPh' fi or CH2Ph*NE*C< N(CH,Ph) N ' C B ,Ph*NH* C< arises from the action of boiling benzylic chloride on anhydrous amido- tetrazole, and is also obtained :is a bye-product in the preparation of a-benzylamidotetrazole ; i t separates from alcohol arid ether in lus- trous crystals, and melts at 88.5". The substance has an alkaline rcaction.The hiydrochloride crystallises in needles, and melts H t !208-209', and the nitrafe at, 122'; the latter salt and the sdphate, which melts a t 173", are sparingly eoluble, and the mh*ite crystallises from ether and melts a t 108". The nitrosarnine crystallises in yellow needles melting at 105", nnd when treated with boiling water yields lrenzyZoxllhenzyItelrazole, which crystallises from alcohol in small needles, and melts a t 106'. P-AmidodiBenzylfetl.nzoZe is most conveniently prepared by heating amidotetrasole (5 grams), with caustic potash (IS grams), benzylic chloride (30 grams), and dilute alcohol in a reflux apparatus for two hours, adding a further qnantity of caustic potash (10 grams), and again heating for two hours, or until the odour of benzylic chloride is no longer perceptible ; it is also formed in the preparation of a- and p-benzylamidotetrazole.It ciytallises from alcohol in lustrous needles, and melts at 169-1iO" ; i t is a neutral substance, arid when oxidised in acid solution with potassium permanpanate yield3 benz- aldehyde. The ~iit/-osarnine crystallises from alcoliol in lustrous, yellow plates, and nielts a t 97-98'. Benz~lben~lllidenebenzy ltetrazylhydruzi~~e, C €3 P h:ru'*N (CHZP h ) * CN4.C HzPh , is obtained by reducing the nitrosamine of benzylaniidobenzyltetrazole in alcoholic solution with zinc dust and glacial acetic acid, and treating the base with alcoholic benzaldehyde ; it, is also formed when benzyl- idenetetrazJ-lhydrazine is treated with boiling benzylic chloride.The substance is insoluble in water, and melts a t 98". Ilenzljlidene-p-di- b e ~ ~ z ~ Z t e t ~ a t y l h ~ d r a z ;ne, C H Ph :N*N*CN4( C H,Ph) *, is ob tai ncd by heat- ing a solution of beiizglidenetetrazylhydraeine in caust ic soda with benzylic chloride for several hours ; it crystallises fi*om alcohol in lustrous leaflets, and melts a t 132-133", yielding benzaldehyde when treated with boiling dilute sillphuric acid. a-Reizzylideizebenzyltetritzylhlldrazi?ze crystallises Pro111 alcoh01, and110 ABSTRACTS OF CHENICAL PAPERS. melts at 161" ; the hydroc7iZo~ide, FvIiicli melts a t 246O, is obtained a8 st bye-product in preparing benzylbenzylidenebenzjltetrnzylhydrazine. a-BenzyltetrazyllL?/drazi?~e is obtained by eliminating benzaldehyde Irom the benzylidene derivative by means of boiling hydrochloric acid ; it crystnllises from water in lustrous leaflets, and melts a t 123".The aqueous solution has a strongly reducing action, and yields the benzylidene derivative when treated wi t,h benzaldchyde. The hydyo- chloride crystallises in long needles, and melts and decomposes at 200". p- Benzylidenebenzyltetrazylhydrazzhe is prepared by heating ben- zylidenetetrazylhydrazine (2 grams) with sodium carbonate ( 1 gram), benzylic chloride (1.3 gram), and a small quantity of water and alcohol; it crystallises from alcohol and melts a t 199'. Boiling mineral acids resolve the substance in to benznldehyde and P-benzyl- t et.razy1 hydrazin e. a - T ~ i b e n z y l t e t ~ a z ~ l l i ~ d m r i ~ ~ e is a bye-product in the formation of Benzylidene-~-dibenzyltetrazylhydrazine, and also arises from treat- ment of tetrazylhydrazine in alkaline solubion with benzylic chloride ; i t crystallises from ethylic acetate in white needles melticg a t 1 5 3 O , and is indifferent towards boiling dilute sulphuric acid.p-l'ribenzyltetrazylIrycE,.aziiLe ia obtained by heating benzglidenetetr- azylhydrazine (2 grams) with benzylic chloride ( 5 grams) and a 25 per cent. solution of caustic soda (10 c.c.), benzaldebyde being elimi- nated. It melts at 121", and is insoluble in acids and alkalis, under- going no change when heated with these agents, 31. 0. F. Effect of Light on Diastase. By JOSEPH R. GREEN (Ann. Agron., 1895, 21, 442-443; from Annals of Bot., 1894, 8, 370).- Sunlight and electric light destroy diastase, the violet rays of the spectrum having thc grcatest eflect, whilst on the other hand, the less refrangible rays have a slightly favourable effect ; the colouring matter of the covering of barley thus protects the diastase from injury by light.Diastase which has been exposed to light, and afterwards kept in darkness, gradually loses its power, the destructive action induced by light continuing. Maltase and the Alcoholic Fermentation of Maltose. By E a m r ; : BOURQUELOT (J. Pharnz., 1895, [GI, 2, 97-103) .-The question whether the enzyme, by which maltose is hydrolysed into glucose, is R chemical individual distinct from the known enzymes, such as dias- tase and invertase, has not j e t been decided. It certainly has not been obtained in a state of purity, for the various preparations that have been made, although possessing the common propevty of hydro- lysing maltose, differ in their powers of hydrolysing other carbohy- drates ; but it is hardly likely, as E.Fischer seems to suppose, that there are many inaltohydrolytic enzymes differing in their powers of hydrolysing other carbohydrates, for all the well-known enzymes of this class are characterised by the limitation of their powers t o the hydrolysis of single carbohydrates. It is now fully established that there is a inaltohydrolytic enzjme in the pancreas and small intestine of various animals, but the ques- N. H. J. &I.ORGANIC CHEMISTRY, 111 tion of the presence of such an enzyme in plants has not hitherto been investigated.The author finds that when the colninoii moulds, Aspe,*gilZus )tiger and PeiiiciZZizirn ghucurn, are cultivatcd in a n aqueous medium containing maltose, with tartaric acid and the usual salts, a, considerable amount of the maltose is hydroljsed into glucose; and by .grinding the moulds with sand, and extracting them with water, liquids can be obtained, from which a maltohydrolytic enzymc is precipitated by alcohol. The lactic fermentation of maltose, like the alcoholic fermentation, is preceded by its hydrolysis ; Fischer’s isolation of glncosazone in the latter case is conclusive, and the author has proved the presence of glucose indirectly in the former case. When chloroform is added t o x solution of maltose, OY of a mixture of maltose and levulose, in alcoholic fermentation, the reducing power of the liquid continues t o increase, whilst the rotatory power diminishes, and this can only be due to the continued formation of glucose by the hydrolytic action of an enzyme, during the suspension of the activity of the yeast. With regard to the presence of a similw enzyme in blood, Dubourg (Inazcg. L h s . , Paris, 1889) has proved that the blood of rabbits kept on an amylaceous diet has the power of hydrolysing maltose. It is thus clear that the assimilation of maltose in animals is always pre- ceded by its hydrolysis into glucose. The author inclines to the opinion that the maltohydrolytic enzyme, maltasc, is a chemical individnal distinct from the other well-known enzymes. JN. W. Preparation of Crystalline Bile acids and their Relation- ship t o Colouring Matters. By RICHTER (Chem. Centr., 1895, i, 282-283; from Deut. Med. Woch., 1894, 21; Vereinsbeilnge, i, 2-3). -Ox bile (250 c.c.) is treated with concenti*ated ferric chloride solution (10-15 c.c.), .and the precipitate dissolved in sulphuric acid (60 per cent.) ; the residue consists chiefly of glycocholic acid; the solution, which contains the taurocholic acid, is f’reed from iron by means of ammonia, the filtrate diluted, sulphuric acid (10 per cent.) added until a precipitate is formed, and then shaken with ether, after 24 hours, crystals of practically pure glycocholic (Y taurocholic) acid are deposited. The two acids may be separated by dissolving them in soda, and acidifying with sulphuric acid ; glycocholic acid is first precipitated, and the taurocholic acid is then deposited as an oil wliicli erystallises after some time. VJhen these acids are treated by Hoppe- S2yler’s method mi th ammol;ia and concentrated sulphuric acid, and the fluorescent product exposed to air, shaken with chloroform, and water added, a violet colour is produced ; this, on fnrther dilution, becomes deep blue, and then changes spontaneously to green. The colours are stable in the dark, but are affected by light., and theii. spectra resemble those of bile pigments. Human bile, and that of an ox suffering from jaundice, gave similar results, but. the glyco- cholic acid appears to be absent. Constitution of Vegetable Proteids. BY € ~ L E C. A. FLGURENT (Compt. rend., 1895, 121, 216--219).-Vegetable proteids can be J. B. T.112 ABSTRACTS OF CHEMICAL PAPERS. divided into two groups, namelg, those, such as gluten, case'in, and vegetable fibrin, in which the ratio of ammoniacal nitrogen estimated to that calculated is greater than uuity, and those, such as legumin and vegetable albumia, in which the ratio is less than unity. The fixed residue from gluten, after boiling with barium hydroxide solu- tioii (Abstr., 1894, i, 214), consists mainly of tryrosine, the caproic leucine, and the leucine, C4H7N02, whilst the fixed residue from legurnin is a mixture of tryrosine, alanine, butalanine, and the diffe- i*ent glucoproteins. I n both animal and vegetable proteids, the water necessary for hydrolysis combines pa,rtly with special groups yielding ammonia, and carbonic, oxalic, and acetic acids, and partly with a special nucleus, yielding a fixed residue. The formula of the fixed residue from vegetable prote'ids, expressed in the simplest general terms, is C,rI12rrN'LOb, whilst that from animal proteids is C,,H211N204. The nucleus of all the vegetable prote'ids examined can be represented by the genernl formula C,lH2,,-dN203, wbilst Schiitzen- berger found for the nucleus o i egg albumin and its congeners the formula CnH2,r--4N202. There is therefore a difference of an atom of oxygen. Ir, both cases, as many molecules of water are necessary to I~ydrolysis as there a1.e atoms of nitrogen present ; in both cases also, liydrolysis takes place in two stages, and it follows that the nucleus of vegetable proteids is a mixture of imido-compounds, which are converted by hrdrolysis into amido-acids. Gluten, case'in, and vege- table fibrin contain a glutamine group, whilst legurnin a.nd vegetable albumin contain an asparagine group (Abstr., 1894, i, 571), and to these respectively is due the departure from unity of the ratios between the found and calculated quant'ities of ammoniacnl nitrogen. The glutamine and asparagine groups do not exist in animal proteids, and Schiitxenberger has found that the quantities of ammoniacal iiitrogen found and calculated aye identical. These groups are the tirst to undergo hydrolysis, and give rise to the ammonia which is obtained by boiling gluten or legumin with alkali solutions under ordinary pressure. C. H. B. Albumoses. By H U G O SCHRij'I'TER (Il.lb?~atsh., 1895, 16, 609-618 ; compare Abstr., 1894, i, 2ll).-The method of distinguishing albu- inoses and peptones proposed by Kuhne is valueless, since these substances and their respective salts all give precipitates with an aqueous solution of ammonium sulphate. Albumoses, however, are perfectly differentiated from peptones by their large percenbage oE nitrogen, by their high molecular weight, and by the still morc important fact that they contain sulphur, whiIst peptones contain none. The generally accepted view, that by the action of ferments or acids, albumin is first of all converted into albumoses, and finally into true peptones, is incorrect. As a matter of fact, when albumin is heated with an acid, a direct conversion into peptones, without the formation of albumoses, takes place, and this is con6rmed by the filct that dburnos?s, when tyeated with an acid, are in a great measure decomposed, and give rise to no peptones. G. T. &I.